Intermediate compound for use in production of dihalopropene compound

ABSTRACT

There is disclosed a dihalopropene compound of the formula I: ##STR1## wherein l is an integer of 1 to 5; m is an integer of 1 to 4; R 1  &#39;s and R 2  &#39;s are the same or different and are independently halogen or various other groups; D is oxygen; X&#39;s are the same or different and are independently chlorine or bromine; Y is oxygen; Z, P and Q are the same or different and are independently nitrogen or CH, provided that P and Q are not simultaneously nitrogen, and when Y is sulfur, Z is CH. Also disclosed is an insecticide/acaricide comprising the dihalopropene compound as an active ingredient. The dihalopropene compound exhibits excellent insecticidal/acaricidal action. Further disclosed is an intermediate compound for use in the production of the dihalopropene compound.

This application is a divisional of application Ser. No. 08/325,597,file on Oct. 19, 1994, U.S. Pat. No. 5,530,015 the entire contents ofwhich are hereby incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to a dihalopropene compound, and aninsecticide/acaricide containing the dihalopropene compound as an activeingredient. It also relates to an intermediate compound for use in theproduction of the dihalopropene compound.

DESCRIPTION OF THE RELATED ART

In the Japanese Patent Laid-open Publication Nos. 48-86835/1973 and49-1526/74, it is disclosed that certain propene compounds can be usedas an active ingredient of insecticides.

However, these compounds are not necessarily sufficient as the activeingredient of insecticides/acaricides in view of insecticidal activity.

SUMMARY OF THE INVENTION

Under these circumstances, the present inventors have studiedintensively to find a compound having an excellentinsecticidal/acaricidal activity. As a result, they have found thatparticular dihalopropene compounds have an excellentinsecticidal/acaricidal activity, thereby completing the presentinvention.

That is, the present invention provides a dihalopropene compound of theformula I: ##STR2## wherein l is an integer of 1 to 5; m is an integerof 1 to 4; R¹ is halogen, cyano, acetamido, trifluoroacetamido, nitro,C₁ -C₈ alkyl, C₁ -C₃ haloalkyl, C₁ -C₇ alkoxy, C₁ -C₃ haloalkoxy, C₁ -C₃alkylthio, C₁ -C₃ haloalkylthio, C₃ -C₆ alkenyloxy, C₃ -C₆haloalkenyloxy, C₁ -C₃ hydroxyalkyl, C₂ -C₄ alkenyl, C₂ -C₄ haloalkenyl,C₂ -C₄ alkynyl, C₂ -C₄ haloalkynyl, C₃ -C₆ alkynyloxy, C₃ -C₆haloalkynyloxy, C₂ -C₄ alkoxyalkyl, C₂ -C₄ alkylthioalkyl, C₃ -C₆cycloalkyl, C₅ -C₆ cycloalkenyl, C₃ -C₆ cycloalkyloxy, C₅ -C₆cycloalkenyloxy, phenyl, pyridyloxy, phenoxy or benzyl, the last four ofwhich may be optionally substituted with halogen, C₁ -C₅ alkyl, C₁ -C₃alkoxy, C₁ -C₃ haloalkyl or C₁ -C₃ haloalkoxy, with the proviso thatwhen l is an integer of 2 to 5, R¹ 's are the same or different, or twoadjacent R¹ 's may be combined together at their terminal ends to formtrimethylene, tetramethylene, methylenedioxy, ethylenedioxy orCH═CH--CH═CH; R² is halogen, C₁ -C₅ alkyl, C₁ -C₃ haloalkyl, C₁ -C₃alkoxy, C₁ -C₃ haloalkoxy, C₂ -C₄ alkenyl, C₂ -C₄ haloalkenyl, C₂ -C₄alkynyl, C₂ -C₄ haloalkynyl, C₂ -C₄ alkoxyalkyl, C₂ -C₄ alkoxyimino,allyloxyimino, nitro or phenyl which may be optionally substituted withhalogen, C₁ -C₅ alkyl or C₁ -C₃ alkoxy, with the proviso that when m isan integer of 2 to 4, R² 's are the same or different, or two adjacentR² 's may be combined together at their terminal ends to formtrimethylene or tetramethylene; D is oxygen, NH or sulfur; X's are thesame or different and are independently chlorine or bromine; Y isoxygen, NR³, S(O)q, C(R⁴)₂, C═C(R⁴)₂ or C(CF₃)₂, wherein R³ is hydrogen,C₁ -C₂ alkyl, trifluoroacetyl or acetyl, R⁴ 's are the same or differentand are independently hydrogen or C₁ -C₃ alkyl, and q is an integer of 0to 2; Z, P and Q are the same or different and are independentlynitrogen or CH, with the proviso that P and Q are not simultaneouslynitrogen, and when Y is sulfur, Z is CH, and an insecticide/acaricidecontaining the dihalopropene compound as an active ingredient.

It is another object of the present invention to provide intermediatecompounds for use in the production of the above dihalopropene compound.

DESCRIPTION OF THE INVENTION

For the substituents R^(l) and R², examples of the halogen are fluorine,chlorine, bromine and iodine.

For the substituent R¹, examples of the C₁ -C₈ alkyl are methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,isopentyl, neopentyl, tert-pentyl, n-hexyl, n-heptyl, tert-octyl,3-n-pentyl and the like.

For the substituents R¹ and R², examples of the C₁ -C₃ haloalkyl aretrifluoromethyl, difluoromethyl, bromodifluoromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl,1-fluoroethyl, 1-chloroethyl, 1-bromoethyl,3,3,3,2,2-pentafluoro-n-propyl, 3,3,3-trifluoro-n-propyl,1-fluoro-n-propyl, 2-chloro-n-propyl, 3-bromo-n-propyl and the like.

For the substituent R¹, examples of the C₁ -C₇ alkoxy are methoxy,ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy,tert-butoxy, n-pentyloxy, isopentyloxy, neopentyloxy, tert-pentyloxy,3-n-pentyloxy, n-hexyloxy, n-heptyloxy and the like.

For the substituents R^(l) and R², examples of the C₁ -C₃ haloalkoxy aretrifluoromethoxy, difluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy,2,2,2-trifluoroethoxy, 2-chloroethoxy,2-bromoethoxy,2-chloro-1,1,2-trifluoroethoxy, 2-bromo-1,1,2-trifluoroethoxy,1,1,2,2-tetrafluoroethoxy, 3,3,3,2,2,1-hexafluoro-n-propoxy,3-fluoro-n-propoxy, 3-chloro-n-propoxy, 3-bromo-n-propoxy,3,3,3,2,2-pentafluoro-n-propoxy, 3,3,3-n-propoxy,2,2,2,1,1-pentafluoroethoxy and the like.

For the substituent R¹, examples of the C₁ -C₃ alkylthio are methylthio,ethylthio, n-propylthio, isopropylthio and the like.

For the substituent R¹, examples of the C₁ -C₃ haloalkylthio aretrifluoromethylthio, difluoromethylthio, bromodifluoromethylthio,2,2,2-trifluoroethylthio, 2-chloro-1,1,2-trifluoroethylthio,2-bromo-1,1,2-trifluoroethylthio, 1,1,2,2-tetrafluoroethylthio,2-chloroethylthio, 2-fluoroethylthio, 2-bromoethylthio,3-fluoro-n-propylthio, 3-chloro-n-propylthio, 3-bromo-n-propylthio,3,3,3,2,2-pentafluoro-n-propylthio, 3,3,3-trifluoro-n-propylthio and thelike.

For the substituent R₁, examples of the C₃ -C₆ alkenyloxy are allyloxy,2-methylallyloxy, 2-butenyloxy, 3-methyl-2-butenyloxy,2-methyl-2-butenyloxy, 2-pentenyloxy, 2-hexenyloxy and the like.

For the substituent R¹, examples of the C₃ -C₆ haloalkenyloxy are3,3-dichloroallyloxy, 3,3-dibromoallyloxy, 2,3-dichloroallyloxy,2,3-dibromoallyloxy, 2-chloro-2-propenyloxy, 3-chloro-2-propenyloxy,2-bromo-2-propenyloxy, 3-chloro-2-butenyloxy and the like.

For the substituent R¹, examples of the C₁ -C₃ hydroxyalkyl arehydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxy-n-propyl,2-hydroxy-n-propyl, 1-hydroxy-n-propyl and the like.

For the substituents R¹ and R², examples of the C₂ -C₄ alkenyl arevinyl, isopropenyl, n-1-propenyl, 2-methyl-1-propenyl,1-methyl-1-propenyl, allyl, 2-methylpropenyl, 2-n-butenyl and the like.

For the substituents R¹ and R², examples of the C₂ -C₄ haloalkenyl are2,2-dichloroethenyl, 2,2-dibromoethenyl, 3,3-dichloroallyl,3,3-dibromoallyl, 2,3-dichloroallyl, 2,3-dibromoallyl,2-chloro-2-propenyl, 3-chloro-2-propenyl, 2-bromo-2-propenyl,3-chloro-2-butenyl and the like.

For the substituents R¹ and R², examples of the C₂ -C₄ alkynyl areethynyl, 1-propynyl, 2-propenyl, 1-methyl-2-propynyl and the like.

For the substituents R₁ and R², examples of the C₂ -C₄ haloalkynyl arechloroethynyl, bromoethynyl, iodoethynyl, 3-chloro-2-propynyl,3-bromo-2-propynyl, 3-iodo-2-propynyl, 1-methyl-3-chloro-2-propynyl,1-methyl-3-bromo-2-propynyl, 1-methyl-3-iodo-2-propynyl and the like.

For the substituent R¹, examples of the C₃ -C₆ alkynyloxy are2-propynyloxy, 1-methyl-2-propynyloxy, 3-butynyloxy, 2-hexynyloxy,3-hexynyloxy, 2-methyl-3-bytynyloxy, 1-methyl-3-bytynyloxy and2-pentynyloxy.

For the substituent R₁, examples of the C₃ -C₆ haloalkynyloxy are3-chloro-2-propynyloxy, 3-bromo-2-propynyloxy,1-methyl-3-chloro-2-propynyloxy, 1-methyl-3-bromo-2-propynyloxy,4-chloro-3-bytynyloxy, 4-bromo-3-bytynyloxy,2-methyl-4-chloro-3-butynyloxy, 2-methyl-4-bromo-3-butynyloxy,1-methyl-4-chloro-3-butynyloxy and 1-methyl-4-bromo-3-butynyloxy.

For the substituents R¹ and R², examples of the C₂ -C₄ alkoxyalkyl aremethoxymethyl, ethoxymethyl, n-propyloxymethyl, isopropyloxymethyl,2-methoxyethyl, 1-methoxyethyl, 2-ethoxyethyl, 1-ethoxyethyl,3-methoxy-n-propyl, 2-methoxy-n-propyl, 1-methoxy-n-propyl,2-methoxy-1-methylethyl and the like.

For the substituent R₁, examples of the C₂ -C₄ alkylthioalkyl aremethylthiomethyl, ethylthiomethyl, n-propylthiomethyl,isopropylthiomethyl, 2-methylthioethyl, 1-methylthioethyl,2-ethylthioethyl, 1-ethylthioethyl, 3-methylthio-n-propyl,2-methylthio-n-propyl, 1-methylthio-n-propyl, 2-methylthio-1-methylethyland the like.

For the substituent R¹, examples of the C₃ -C₅ cycloalkyl arecyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

For the substituent R₁, examples of the C₅ -C₆ cycloalkenyl are1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-cyclohexenyl,2-cyclohexenyl, 3-cyclohexenyl and the like.

For the substituent R¹, examples of the C₃ -C₆ cycloalkyloxy arecyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy and thelike.

For the substituent R¹, examples of the C₅ -C₆ cycloalkenyloxy are1-cyclopentenyloxy, 2-cyclopentenyloxy, 3-cyclopentenyloxy,1-cyclohexenyloxy, 2-cyclohexenyloxy, 3-cyclohexenyloxy and the like.

Examples of the C₁ -C₅ alkyl group which may be optionally present onthe phenyl or phenoxy for the substituents R₁ and/or R² are methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,n-pentyl, isopentyl, neopentyl, tert-pentyl and the like.

When R¹ and R² are independently phenyl, pyridyloxy, benzyl or phenoxy.all of which may be optionally substituted with C₁ -C₃ alkoxy, examplesof the C₁ -C₃ alkoxy are methoxy, ethoxy, n-propoxy and i-propoxy.

For the substituent R², examples of the C₂ -C₄ alkoxyimino aremethoxyimino, ethoxyimino, n-propoxyimino, isopropoxyimino and the like.

Examples of the C₁ -C₅ alkoxy which may be optionally present on thephenyl for the substituent R² are methoxy, ethoxy, n-propyloxy,isopropyloxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy,3-n-pentyloxy, isopentyloxy, neopentyloxy, tert-pentyloxy group and thelike.

For the substituent R³, examples of the C₁ -C₃ alkyl are methyl,n-propyl, ethyl, isopropyl group and the like.

For the substituents R⁴ and R⁵, examples of the C₁ -C₂ alkyl are methylor ethyl.

Among the dihalopropene compounds of the present invention, preferablecompounds are those defined as follows: R¹ is halogen, C₁ -C₈ alkyl, C₁-C₃ haloalkyl, C₁ -C₇ alkoxy, C₁ -C₃ haloalkoxy, C₃ -C₆ alkenyloxy, C₃-C₆ haloalkenyloxy, C₃ -C₆ cycloalkyl, phenyl, pyridyloxy, phenoxy orbenzyl, the last four of which may be optionally substituted withhalogen C₁ -C₅ alkyl, C₁ -C₃ alkoxy, C₁ -C₃ haloalkyl or C₁ -C₃haloalkoxy, with the proviso that when l is an integer of 2 to 5, R¹ 'sare the same or different, or two adjacent R¹ 's may be combinedtogether at their terminal ends to form trimethylene, tetramethylene,methylenedioxy, ethylenedioxy or CH═CH--CH═CH; R² is halogen, nitro, C₁-C₅ alkyl, C₁ -C₃ haloalkyl, C₂ -C₄ alkenyl, C₂ -C₄ haloalkenyl, C₂ -C₄alkynyl, C₂ -C₄ alkoxyalkyl, C₂ -C₄ alkoxyimino, allyloxyimino or phenylwhich may be optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₃alkoxy, with the proviso that when m is an integer of 2 to 4, R² 's arethe same or different, or two adjacent R² 's may be combined together attheir terminal ends to form trimethylene or tetramethylene; D is oxygen;X's are the same or different and are independently chlorine or bromine;Y is oxygen, NR³, sulfur or C(R⁴)₂, wherein R³ is hydrogen or C₁ -C₂alkyl and R⁴ 's are the same or different and are independently hydrogenor C₁ -C₃ alkyl; Z is nitrogen or CH, with the proviso that when Y issulfur, Z is CH; P and Q are CH.

More preferably, when Z is CH, R¹ is halogen, C₁ -C₈ alkyl,trifluoromethyl, C₁ -C₂ haloalkoxy, C₁ -C₄ alkoxy, C₃ -C₅ alkenyloxy, C₃-C₄ haloalkenyloxy, cyclohexyl, cyclopentyl, phenyl, phenoxy orpyridyloxy which may be optionally substituted with halogen, C₁ -C₄alkyl or trifluoromethyl, with the proviso that when l is an integer of2 or 3, R¹ 's are the same or different, or two adjacent R¹ 's may becombined together at their terminal ends to form trimethylene,tetramethylene, methylenedioxy, ethylenedioxy or CH═CH--CH═CH; and whenZ is nitrogen, R¹ is halogen, trifluoromethyl or nitro; R² is halogen,C₁ -C₄ alkyl, trifluoromethyl, C₃ -C₄ alkenyl, C₃ -C₄ haloalkenyl,ethynyl, methoxymethyl, nitro, C₁ -C₂ alkoxyimino, allyloxyimino orphenyl, with the proviso that m is an integer of 2 or 3, R² 's are thesame or different, or two adjacent R² 's may be combined together attheir terminal ends to form tetramethylene; D is oxygen; X's are thesame or different and are independently chlorine or bromine; when Z isCH, Y is oxygen, NR³, sulfur or C(CH₃)₂, wherein R³ is as defined above,and when Z is nitrogen, Y is oxygen or NH; P and Q are CH.

Most preferably, when Z is CH, l is an integer 1 to 3 R¹ is halogen, C₁-C₂ haloalkyl, C₃ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₃ haloalkoxy,cyclohexyl, cyclopentyl, phenyl or phenoxy, with the proviso that when lis an integer of 2 or 3, R¹ 's the same or different, or two adjacent R¹'s may be combined together at their terminal ends to formtetramethylene, methylenedioxy or CH═CH--CH═CH, and R² is halogen,trifluoromethyl, allyl or C₃ alkyl; and when Z is hitrogen, m is aninteger of 1 or 2 R¹ is halogen or trifluoromethyl, and R² is halogen ormethyl, with the proviso that when m is an integer of 1 or 2 R² 's arethe same or different, D is oxygen; X's are the same or different andare independently chlorine or bromine; when Z is CH, Y is oxygen, sulfuror C(CH₃)₂, and when Z is nitrogen, Y is oxygen or NH; P and Q are CH.

The dihalopropene compounds of the present invention can be produced bythe following production processes.

Production process A

The process A for producing the dihalopropene compounds of the presentinvention comprises reacting a compound of the formula II: ##STR3##wherein R¹ R², Y, D, Z, P, Q, l and m are each as defined above, with acompound of the formula III:

    L--CH.sub.2 CH═CX.sub.2                                (III)

wherein X is as defined above; and L is halogen such as chlorine,bromine or iodine, mesyloxy or tosyloxy.

The raw material compound of the formula II is obtained by conventionalproduction processes as depicted in the Schemes below, and examples ofthe intermediates are also listed therein.

The intermediate compounds include novel compounds of the formula:##STR4## wherein R¹ is halogen, C₁ -C₈ alkyl, C₁ -C₃ haloalkyl, C₁ -C₄alkoxy, C₁ -C₂ haloalkoxy, C₃ -C₅ alkenyloxy, C₃ -C₄ haloalkenyloxy, C₃-C₆ cycloalkyl, phenyl, pyridyloxy, phenoxy or benzyl, the last four ofwhich may be optionally substituted with halogen or C₁ -C₅ alkyl, C₁ -C₃alkoxy, C₁ -C₃ haloalkoxy or C₁ -C₃ haloalkxyl, with the proviso thatwhen l is an integer of 2 to 5, the R¹ 's are the same or different, andwhen l is an integer of 2 or 3, two adjacent R¹ 's may be combinedtogether at their terminal ends to form trimethylene, tetramethylene,methylenedioxy, ethylenedioxy or CH═CH--CH═CH.

The intermediate compounds further include novel compounds of theformula: ##STR5## wherein R¹ is halogen such as fluorine, chlorine,bromine or iodine, or trifluoromethyl; and R² and R^(2') are the same ordifferent and are independently fluorine, chlorine, trifluoromethyl ormethyl.

Alternatively, the novel intermediate compounds may be of the formula:##STR6## wherein R¹ is halogen such as fluorine, chlorine, bromine oriodine, or trifluoromethyl; R² is halogen, trifluoromethyl or C₁ -C₃alkyl; and m is an integer of 1 to 4.

The above reaction is usually carried out in an inert solvent under thepresence of a suitable base.

Examples of the solvent to be used are ketones such as acetone, methylethyl ketone and cyclohexanone, ethers such as 1,2-dimethoxyethane,tetrahydrofuran, dioxane and C₁ -C₄ dialkyl ether (e.g., diethyl ether,diisopropyl ether), N,N-dimethylformamide, dimethylsulfoxide,hexamethylphosphorous triamide, sulfolane, acetonitrile, nitromethane,halogenated hydrocarbons such as dichloromethane, chloroform,1,2-dichloroethane and chlorobenzene, hydrocarbons such as toluene,benzene and xylene, and water. These solvents can be used alone or incombination.

Examples of the base to be used are hydroxides of alkali metals oralkaline earth metals, such as lithium hydroxide, sodium hydroxide,potassium hydroxide and calcium hydroxide; carbonates of alkali metalsor alkaline earth metals, such as lithium carbonate, sodium carbonate,potassium carbonate and calcium carbonate; hydrides of alkali metals oralkaline earth metals, such as lithium hydride, sodium hydride,potassium hydride and calcium hydride; C₁ -C₄ alkoxides of alkalimetals, such as sodium methoxide, sodium ethoxide and potassiumtert-butoxide; organic bases such as triethylamine and pyridine. Ifnecessary, a catalyst such as an ammonium salt (e.g.,triethylbenzylammonium chloride) may be added to the reaction system inan proportion of 0.01 to 1 mole to 1 mole of the compound II.

The reaction temperature may be usually in the range of from -20° C. tothe boiling point of a solvent used for the reaction or 150° C., morepreferably from -5° C. to the boiling point of the solvent used for thereaction or 100° C.

The molar ratio of the raw material and base to be used for the reactioncan optionally be set, but it is advantageous to conduct the reactionusing them in the equimolar ratio or in a ratio similar thereto.

After completion of the reaction, the reaction solution can be subjectedto ordinary post-treatments such as organic solvent extraction and/orconcentration to isolate the desired compound. If necessary, theresultant compound can be purified by a method such as chromatography orrecrystallization.

Production process B

The process B for producing the dihalopropene compound of the presentinvention comprises reacting the compound of the formula II with analcohol compound of the formula IV:

    HO--CH.sub.2 CH═CX.sub.2                               (IV)

wherein X is as defined above.

It is preferred that the above reaction is carried out in an inertsolvent under the presence of a suitable dehydrating agent.

Examples of the dehydrating agent are dicyclohexylcarbodiimide, di(C₁-C₄ alkyl)azodicarboxylate (e.g., diethylazodicarboxylate,diisopropylazodicarboxylate), tri(C₁ -C₂₀ alkyl)phosphine ortriarylphosphine (e.g., triphenylphosphine, trioctylphosphine,tributylphosphine) and the like.

Examples of the solvent to be used are hydrocarbons such as benzene,xylene and toluene; ethers such as diethyl ether, diisopropyl ether,tetrahydrofuran and dioxane; halogenated hydrocarbons such as carbontetrachloride, dichloromethane, chlorobenzene and dichlorobenzene.

The reaction temperature may be usually in the range of from -20° C. to200° C. or the boiling point of a solvent used for the reaction.

The molar ratio of the raw material and dehydrating agent to be used forthe reaction can optionally be set, but it is advantageous to conductthe reaction using them in the equimolar ratio or in a ratio similarthereto.

After completion of the reaction, the reaction solution can be subjectedto ordinary post-treatments such as organic solvent extraction and/orconcentration to isolate the desired compound. If necessary, theresultant compound can be purified by a method such as chromatography orrecrystallization.

Production process C (when D is an oxygen atom in the dihalopropenecompound of the present invention):

The production process C for producing the dihalopropene compound of thepresent invention comprises reacting an aldehyde compound of the formulaV: ##STR7## wherein R¹, R², Y, Z, P, Q, l and m are each as definedabove, with carbon tetrachloride or carbon tetrabromide.

It is preferred that the above reaction is carried out in an inertsolvent under the presence of a suitable trialkylphosphine ortriarylphosphine, if necessary, under the presence of metallic zinc.

Examples of the solvent to be used are hydrocarbons such as benzene,xylene and toluene; ethers such as diethyl ether, diisopropyl ether,tetrahydrofuran and dioxane; halogenated hydrocarbons such asdichloromethane, 1,2-dichloroethane and chlorobenzene (excluding carbontetrabromide and carbon tetrachloride).

The reaction temperature may be usually in the range of from -30° C. tothe boiling point of a solvent used for the reaction or 150° C.

Examples of the (C₁ -C₂₀ trialkyl)phosphine or triarylphosphine aretriphenylphosphine, trioctylphosphine and the like. It is preferred thatmetallic zinc optionally used is in a dust form.

The molar ratio of the raw material and reagent to be used for thereaction can optionally be chosen. The proportion of carbon tetrabromide(tetrachloride), trialkylphosphine or triarylphosphine and metallic zincis 2 moles, 2 or 4 moles and 2 moles, respectively, to 1 mole of thealdehyde compound of the formula V.

After completion of the reaction, the reaction solution can be subjectedto ordinary post-treatments such as organic solvent extraction and/orconcentration to isolate the desired compound. If necessary, theresultant compound can be purified by a method such as chromatography orrecrystallization.

If the dihalopropene compound of the present invention contains anasymmetric atom, the corresponding optically-active isomers havingbiological activity (e.g., (+)-isomer, (-)-isomer) and mixtures of theseisomers in any ratio are also included in the present invention.

Some examples of the present dihalopropene compound of the presentinvention will be shown below; however, the present invention is notlimited thereto.

The compound of the following formulae VI-1 to VI-6 are shown in Table1.

                  TABLE 1                                                         ______________________________________                                         ##STR8##                                                                      ##STR9##                                                                      ##STR10##                                                                     ##STR11##                                                                     ##STR12##                                                                     ##STR13##                                                                    ______________________________________                                        (R.sup.1).sub.l (R.sup.1).sub.l                                               ______________________________________                                        2-F             2,3,4-Cl.sub.3                                                3-F             2,3,6-Cl.sub.3                                                4-F             2,4,6-Cl.sub.3                                                2,3-F.sub.2     2,3,5-Cl.sub.3                                                3,4-F.sub.2     2,4,5-Cl.sub.3                                                2,6-F.sub.2     2,3,4,5,6-Cl.sub.3                                            2,4-F.sub.2     2-Br                                                          2,5-F.sub.2     3-Br                                                          3,5-F.sub.2     4-Br                                                          2,3,4-F.sub.3   3,5-Br.sub.2                                                  2,3,6-F.sub.3   2,4-Br.sub.2                                                  2,3,5-F.sub.3   2-I                                                           2,4,5-F.sub.3   3-I                                                           2,3,5,6-F.sub.4 4-I                                                           2,3,4,5,6-F.sub.5                                                                             2-F, 4-Cl                                                     2-Cl            3-F, 4-Cl                                                     3-Cl            3-Cl, 4-F                                                     4-Cl            2-Br, 4-F                                                     2,3-Cl.sub.2    2-F, 4-Br                                                     2,6-Cl.sub.2    2-Br, 5-F                                                     3,5-Cl.sub.2    2-Br, 4-Cl                                                    2,4-Cl.sub.2    2-Cl, 4-F                                                     3,4-Cl.sub.2    2-Cl, 4-Br                                                    2,5-Cl.sub.2    3-CH.sub.3                                                    2-Cl, 4-OCH.sub.3                                                                             3-C.sub.2 H.sub.5                                             3-CH.sub.3, 4-Cl                                                                              3-CH(CH.sub.3).sub.2                                          2-CH.sub.3, 4-F 3-C(CH.sub.3).sub.3                                           3-CH.sub.3, 4-F 3-CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                         2-Cl, 4-CH.sub.3                                                                              3-CH(CH.sub.3)CH.sub.2 CH.sub.3                               2-Cl, 5-CH.sub.3                                                                              3-CH.sub.2 CH(CH.sub.3).sub.2                                 2-CH.sub.3, 4-Cl                                                                              3-(CH.sub.2).sub.4 CH.sub.3                                   3-C.sub.2 H.sub.5, 4-Cl                                                                       3-CH(CH.sub.3)(CH.sub.2).sub.2 CH.sub.3                       2-Br, 4-CH.sub.3                                                                              3-CH(CH.sub.3)CH(CH.sub.3).sub.2                              2-CH.sub.3, 4-I 3-CH(C.sub.2 H.sub.5).sub.2                                   2-Cl, 5-CF.sub.3                                                                              3-C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3                         2,4-Cl.sub.2, 3-CH.sub.3                                                                      3-(CH.sub.2).sub.5 CH.sub.3                                   4-Cl, 3,5-(CH.sub.3).sub.2                                                                    3-(CH.sub.2).sub.6 CH.sub.3                                   4-Br, 3,5-(CH.sub.3).sub.2                                                                    3-(CH.sub.2).sub.7 CH.sub.3                                   4-Br, 2,6-(CH.sub.3).sub.2                                                                    4-CH.sub.3                                                    4-Cl, 4,5-(CH.sub.3).sub.2                                                                    4-C.sub.2 H.sub.5                                             2-CH(CH.sub.3).sub.2, 4-Cl, 5-CH.sub.3                                                        4-CH.sub.2 CH.sub.2 CH.sub.3                                  2-CH.sub.3      4-CH(CH.sub.3).sub.2                                          2-C.sub.2 H.sub.5                                                                             4-(CH.sub.2).sub.3 CH.sub.3                                   2-CH.sub.2 CH.sub.2 CH.sub.3                                                                  4-CH(CH.sub.3)CH.sub.2 CH.sub.3                               2-CH(CH.sub.3).sub.2                                                                          4-CH.sub.2 CH(CH.sub.3).sub.2                                 2-CH(CH.sub.3)CH.sub.2 CH.sub.3                                               2-C(CH.sub.3).sub.3                                                                           4-C(CH.sub.3).sub.3                                           4-(CH.sub.2).sub.4 CH.sub.3                                                                   2-Br, 4-(CH.sub.2).sub.2 CH.sub.3                             4-CH(CH.sub.3)(CH.sub.2).sub.2 CH.sub.3                                                       2-Br, 4-CH(CH.sub.3).sub.2                                    4-CH(CH.sub.3)CH(CH.sub.3).sub.2                                                              2-Br, 4-(CH.sub.2).sub.3 CH.sub.3                             4-CH(C.sub.2 H.sub.5).sub.2                                                                   2-Br, 4-CH(CH.sub.3)CH.sub.2 CH.sub.3                         4-C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3                                                         2-Br, 4-CH.sub.2 CH(CH.sub.3).sub.2                           4-(CH.sub.2).sub.5 CH.sub.3                                                                   2-Br, 4-C(CH.sub.3).sub.3                                     4-(CH.sub.2).sub.6 CH.sub.3                                                                   2-Br, 4-(CH.sub.2).sub.4 CH.sub.3                             4-(CH.sub.2).sub.7 CH.sub.3                                                                   2-Br, 4-CH(CH.sub.3)(CH.sub.2).sub.2 CH.sub.3                 4-C(CH.sub.3).sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                2-Br, 4-CH(CH.sub.3)CH(CH.sub.3).sub.2                        2-Cl, 4-C.sub.2 H.sub.5                                                                       2-Br, 4-CH(C.sub.2 H.sub.5).sub.2                             2-Cl, 4-CH.sub.2 CH.sub.2 CH.sub.3                                                            2-Br, 4-C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3                   2-Cl, 4-CH(CH.sub.3).sub.2                                                                    2-CF.sub.3                                                    2-Cl, 4-(CH.sub.2).sub.3 CH.sub.3                                                             3-CF.sub.3                                                    2-CJ, 4-CH(CH.sub.3)CH.sub.2 CH.sub.3                                                         4-CF.sub.3                                                    2-Cl, 4-CH.sub.2 CH(CH.sub.3).sub.2                                                           3,5-(CF.sub.3).sub.2                                          2-Br, 4-CH.sub.2 CH(CH.sub.3).sub.2                                                           2,4-(CF.sub.3).sub.2                                          2-Br, 4-CH.sub.2 CH(CH.sub.3).sub.2                                                           2-F, 4-CF.sub.3                                               2-Cl, 4-C(CH.sub.3).sub.3                                                                     2-Cl, 4-CF.sub.3                                              2-Cl, 4-(CH.sub.2).sub.4 CH.sub.3                                                             2,6-Cl.sub.2, 4-CF.sub.3                                      2-Cl, 4-CH(CH.sub.3)(CH.sub.2).sub.2 CH.sub.3                                                 2-CF.sub.3, 4-Cl                                              2-Cl, 4-CH(CH.sub.3)CH(CH.sub.3).sub.2                                                        2-CF.sub.3, 5-Cl                                              2-Cl, 4-CH(C.sub.2 H.sub.5).sub.2                                                             2-Br, 4-CF.sub.3                                              2-Cl, 4-C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3                                                   2-CF.sub.3, 4-Br                                              2-Br, 4-C.sub.2 H.sub.5                                                                       2-I, 4-CF.sub.3                                               2-F, 6-Cl, 4-CF.sub.3                                                                         3-OCH(CH.sub.3).sub.2                                         2,6-F.sub.2, 4-CF.sub.3                                                                       3-O(CH.sub.2).sub.3 CH.sub.3                                  2-CCl.sub.3     3-OCH(CH.sub.3)CH.sub.2 CH.sub.3                              4-CCl.sub.3     3-OCH.sub.2 CH(CH.sub.3).sub.2                                2-CHF.sub.2     3-OC(CH.sub.3).sub.3                                          3-CHF.sub.2     3-O(CH.sub.2).sub.4 CH.sub.3                                  4-CHF.sub.2     3-OCH(CH.sub.3)(CH.sub.2).sub.2 CH.sub.3                      2-CF.sub.2 Br   3-OCH(C.sub.2 H.sub.5).sub.2                                  3-CF.sub.2 Br   3-OCH(CH.sub.3)CH(CH.sub.3).sub.2                             4-CF.sub.2 Br   3-O(CH.sub.2).sub.5 CH.sub.3                                  3-CH.sub.2 CF.sub.3                                                                           3-O(CH.sub.2).sub.6 CH.sub.3                                  4-CH.sub.2 CF.sub.3                                                                           4-OCH.sub.3                                                   3-CH.sub.2 CH.sub.2 CF.sub.3                                                                  4-OC.sub.2 H.sub.5                                            4-CH.sub.2 CH.sub.2 CF.sub.3                                                                  4-OCH.sub.2 CH.sub.2 CH.sub.3                                 3-CH.sub.2 CF.sub.2 CF.sub.3                                                                  4-OCH(CH.sub.3).sub.2                                         4-CH.sub.2 CF.sub.2 CF.sub.3                                                                  4-O(CH.sub.2).sub.3 CH.sub.3                                  2-OCH.sub.3     4-OCH(CH.sub.3)CH.sub.2 CH.sub.3                              2-OC.sub.2 H.sub.5                                                                            4-OCH.sub.2 CH(CH.sub.3).sub.2                                2-OCH.sub.2 CH.sub.2 CH.sub.3                                                                 4-OC(CH.sub.3).sub.3                                          2-OCH(CH.sub.3).sub.2                                                                         4-O(CH.sub.2).sub.4 CH.sub.3                                  2-OCH(CH.sub.3).sub.2                                                                         4-OCH(CH.sub.3)(CH.sub.2).sub.2 CH.sub.3                      3-OCH.sub.3     4-OCH(CH.sub.3)CH.sub.2 (CH.sub.3).sub.2                      3-OC.sub.2 H.sub.5                                                            3-OCH.sub.2 CH.sub.2 CH.sub.3                                                                 4-OCH(C.sub.2 H.sub.5).sub.2                                  3-OC(CH.sub.3).sub.2 CH.sub.2 CH.sub.3                                                        3,4,5-(OCH.sub.3).sub.3                                       4-OC(CH.sub.3).sub.2 CH.sub.2 CH.sub.3                                                        3-Cl, 5-OCH.sub.3                                             4-O(CH.sub.2).sub.5 CH.sub.3                                                                  2-Cl, 4-OC.sub.2 H.sub.5                                      4-O(CH.sub.2).sub.6 CH.sub.3                                                                  2-Cl, 4-OCH.sub.2 CH.sub.2 CH.sub.3                           3,5-(C(CH.sub.3).sub.3).sub.2                                                                 2-Cl, 4-OCHC(CH.sub.3).sub.2                                  3,5-(CH.sub.3).sub.2                                                                          2-Cl, 4-O(CH.sub.2).sub.3 CH.sub.3                            3-CH.sub.3, 5-CH(CH.sub.3).sub.2                                                              2-Cl, 4-OCH(CH.sub.3)CH.sub.2 CH.sub.3                        3,4-(CH.sub.3).sub.2                                                                          2-Cl, 4-OCH.sub.2 CH(CH.sub.3).sub.2                          2,4-(CH.sub.3).sub.2                                                                          2-Cl, 4-OC(CH.sub.3).sub.3                                    2,5-(CH.sub.3).sub.2                                                                          2-Cl, 4-O(CH.sub.2).sub.4 CH.sub.3                            2-CH(CH.sub.3).sub.2, 5-CH.sub.3                                                              2-Cl, 4-OCH(CH.sub.3)(CH.sub.2).sub.2 CH.sub.3                3-CH.sub.3, 4-CH(CH.sub.3).sub.2                                                              2-Cl, 4-OCH(CH.sub.3)CH(CH.sub.3).sub.2                       2-CH.sub.3, 5-CH(CH.sub.3).sub.2                                                              2-Cl, 4-OCH.sub.2 CH(C.sub.2 H.sub.5).sub.2                   2-C(CH.sub.3).sub.3, 5-CH.sub.3                                                               2-Cl, 4-OC(CH.sub.3).sub.2 CH.sub.2 CH.sub.3                  2-C(CH.sub.3).sub.3, 4-CH.sub.3                                                               2-Br, 4-OCH.sub.3                                             2,4-(C(CH.sub.3).sub.3).sub.2                                                                 2-Br, 4-OC.sub.2 H.sub.5                                      2,3,5-(CH.sub.3).sub.3                                                                        2-Br, 4-O(CH.sub.2).sub.2 CH.sub.3                            3,4,5-(CH.sub.3).sub.3                                                                        2-Br, 4-OCH(CH.sub.3).sub.2                                   2,4,6-(CH.sub.3).sub.3                                                                        2-Br, 4-O(CH.sub.2).sub.3 CH.sub.3                            2,3-(OCH.sub.3).sub.2                                                                         2-Br, 4-OCH(CH.sub.3)CH.sub.2 CH.sub.3                        3,5-(OCH.sub.3).sub.2                                                                         2-Br, 4-OCH.sub.2 CH(CH.sub.3).sub.2                          2-OCH.sub.3, 4-CH.sub.3                                                                       2-Br, 4-OC(CH.sub.3).sub.3                                    3,4-(OCH.sub.3).sub.2                                                                         2-Br, 4-O(CH.sub.2).sub.4 CH.sub.3                            3-C.sub.2 H.sub.5, 4-OCH.sub.3                                                                2-CH.sub.3, 4-OCH(CH.sub.3).sub.2                             2-Br, 4-OCH(CH.sub.3)(CH.sub.2).sub.2 CH.sub.3                                                2,3-(CH.sub.3).sub.2, 4-OCH.sub.3                             2-Br, 4-OCH(CH.sub.3)CH(CH.sub.3).sub.2                                                       2,3-(CH.sub.3).sub.2, 4-OC.sub.2 H.sub.5                      2-Br, 4-OCH(C.sub.2 H.sub.5).sub.2                                                            2,3-(CH.sub.3).sub.2, 4-OCH(CH.sub.3).sub.2                   2-Br, 4-OC(CH.sub.3).sub.2 CH.sub.2 CH.sub.3                                                  2-OCF.sub.3                                                   3-OCH.sub.3, 5-OC.sub.2 H.sub.5                                                               3-OCF.sub.3                                                   3,5-(OC.sub.2 H.sub.5).sub.2                                                                  4-OCF.sub.3                                                   3,5-(OCH(CH.sub.3).sub.2).sub.2                                                               2-OCHF.sub.2                                                  3-OCH.sub.3, 5-OCH(CH.sub.3).sub.2                                                            3-OCHF.sub.2                                                  3-OC.sub.2 H.sub.5, 5-OCH(CH.sub.3).sub.2                                                     4-OCHF.sub.2                                                  2-CH.sub.3, 3-OCH.sub.3                                                                       2-OCF.sub.2 Br                                                2-CH.sub.3, 3-OC.sub.2 H.sub.5                                                                3-OCF.sub.2 Br                                                2-CH.sub.3, 3-OCH(CH.sub.3).sub.2                                                             4-OCF.sub.2 Br                                                2-CH.sub.3, 3-OCH(CH.sub.3).sub.2                                                             3-OCH.sub.2 CF.sub.3                                          3-OCH.sub.3, 4-Cl                                                                             4-OCH.sub.2 CF.sub.3                                          3-OCH.sub.3, 4-Br                                                                             3-OCF.sub.2 CFHCl                                             3-OC.sub.2 H.sub.5, 4-Cl                                                                      4-OCF.sub.2 CFHCl                                             3-OC.sub.2 H.sub.5, 4-Br                                                                      3-OCF.sub.2 CFHBr                                             3-OCH(CH.sub.3).sub.2, 4-Cl                                                                   4-OCF.sub.2 CFHBr                                             3-OCH(CH.sub.3).sub.2, 4-Br                                                                   3-OCF.sub.2 CF.sub.2 H                                        3-CH.sub.3, 5-OCH.sub.3                                                                       4-OCF.sub.2 CF.sub.2 H                                        3-CH.sub.3, 5-OC.sub.2 H.sub.5                                                                3-OCH.sub.2 CH.sub.2 CF.sub.3                                 3-CH.sub.3, 5-OCHC(CH.sub.3).sub.2                                                            4-OCH.sub.2 CH.sub.2 CF.sub.3                                 2-CH.sub.3, 4-OCH.sub.3                                                       2-CH.sub.3, 4-OC.sub.2 H.sub.5                                                                3-OCH.sub.2 CF.sub.2 CF.sub.3                                 4-OCH.sub.2 CF.sub.2 CF.sub.3                                                                 2-SCF.sub.3                                                   2-Cl, 4-OCF.sub.3                                                                             3-SCF.sub.3                                                   2-Cl, 4-OCHF.sub.2                                                                            4-SCF.sub.3                                                   2-Cl, 4-OCF.sub.2 Br                                                                          3-SCHF.sub.2                                                  2-Cl, 4-OCH.sub.2 CF.sub.3                                                                    4-SCHF.sub.2                                                  2-Cl, 4-OCH.sub.2 CH.sub.2 CF.sub.3                                                           3-SCF.sub.2 Br                                                2-Cl, 4-OCH.sub.2 CF.sub.2 CF.sub.3                                                           4-SCF.sub.2 Br                                                2-Cl, 4-OCF.sub.2 CF.sub.2 H                                                                  3-SCH.sub.2 CF.sub.3                                          2-Cl, 4-OCF.sub.2 CFHCl                                                                       4-SCH.sub.2 CF.sub.3                                          2-Cl, 4-OCF.sub.2 CFHBr                                                                       3-SCF.sub.2 CFHCl                                             3-OCF.sub.2 CF.sub.3                                                                          4-SCF.sub.2 CFHCl                                             4-OCF.sub.2 CF.sub.3                                                                          3-SCF.sub.2 CFHBr                                             2-SCH.sub.3     4-SCF.sub.2 CFHBr                                             3-SCH.sub.3     3-SCF.sub.2 CF.sub.2 H                                        4-SCH.sub.3     4-SCF.sub.2 CF.sub.2 H                                        2-CH.sub.3, 4-SCH.sub.3                                                                       3-SCH.sub.2 CF.sub.2 CF.sub.3                                 2-SC.sub.2 H.sub.5                                                                            4-SCH.sub.2 CF.sub.2 CF.sub.3                                 3-SC.sub.2 H.sub.5                                                                            3-SCH.sub.2 CH.sub.2 CF.sub.3                                 3-SCH.sub.2 CH.sub.2 CH.sub.3                                                                 4-SCH.sub.2 CH.sub.2 CF.sub.3                                 3-SCH(CH.sub.3).sub.2                                                                         3-SCF.sub.2 CF.sub.3                                          4-SC.sub.2 H.sub.5                                                                            4-SCF.sub.2 CF.sub.3                                          4-S(CH.sub.2).sub.2 CH.sub.3                                                                  3-CH.sub.3, 4-SCH.sub.3                                       4-SCH(CH.sub.3).sub.2                                                                         3-OCH.sub.2 CHCH.sub.2                                        3-OCH(CH.sub.3)CHCH.sub.2                                                                     4-OCH.sub.2 CHCH.sub.2                                        4-OCH(CH.sub.3)CHCH.sub.2                                                                     3-OCH.sub.2 C(Br)CH.sub.2                                     3-OCH.sub.2 CHCH(CH.sub.3)                                                                    4-OCH.sub.2 C(Br)CH.sub.2                                     4-OCH.sub.2 CHCH(CH.sub.3)                                                                    3-OCH.sub.2 CHCH(Cl)(CH.sub.3)                                3-OCH.sub.2 CHC(CH.sub.3).sub.2                                                               4-OCH.sub.2 CHCH(Cl)(CH.sub.3)                                4-OCH.sub.2 CHC(CH.sub.3).sub.2                                                               3-CH.sub.2 OH                                                 3-OCH.sub.2 C(CH.sub.3)CHCH.sub.3                                                             4-CH.sub.2 OH                                                 4-OCH.sub.2 C(CH.sub.3)CHCH.sub.3                                                             3-CH(OH)CH.sub.3                                              3-OCH.sub.2 CHCHC.sub.2 H.sub.5                                                               4-CH(OH)CH.sub.3                                              4-OCH.sub.2 CHCHC.sub.2 H.sub.5                                                               3-CH.sub.2 CH.sub.2 OH                                        3-OCH.sub.2 CHCH(CH.sub.2).sub.2 CH.sub.3                                                     4-CH.sub.2 CH.sub.2 OH                                        4-OCH.sub.2 CHCH(CH.sub.2).sub.2 CH.sub.3                                                     3-CH(OH)CH.sub.2 CH.sub.3                                     3-OCH.sub.2 CHCCl.sub.2                                                                       4-CH(OH)CH.sub.2 CH.sub.3                                     4-OCH.sub.2 CHCCl.sub.2                                                                       3-CH.sub.2 CH(OH)CH.sub.3                                     3-OCH.sub.2 CHCBr.sub.2                                                                       4-CH.sub.2 CH(OH)CH.sub.3                                     4-OCH.sub.2 CHCBr.sub.2                                                                       3-CH.sub.2 CH.sub.2 CH.sub.2 OH                               3-OCH.sub.2 C(Cl)CH(Cl)                                                                       4-CH.sub.2 CH.sub.2 CH.sub.2 OH                               4-OCH.sub.2 C(Cl)CH(Cl)                                                                       3-cyclopentyl                                                 3-OCH.sub.2 C(Br)CH(Br)                                                                       4-cyclopentyl                                                 4-OCH.sub.2 C(Br)CH(Br)                                                                       3-cyclohexyl                                                  3-OCH.sub.2 C(Cl)CH.sub.2                                                                     4-cyclohexyl                                                  4-OCH.sub.2 C(Cl)CH.sub.2                                                                     3-phenyl                                                      3-OCH.sub.2 CHCH(Cl)                                                                          4-phenyl                                                      4-OCH.sub.2 CHCH(Cl)                                                                          3-O-cyclopentyl                                               4-O-cyclopentyl 2-Cl, 4-cyclohexyl                                            3-O-cyclohexyl  2-Cl, 4-phenyl                                                4-O-cyclohexyl  2-Cl, 4-cyclohexyl                                            3-phenoxy       2-Cl, 4-O-cyclopentyl                                         4-phenoxy       2-Cl, 4-O-cyclohexyl                                          2-Cl, 4-cyclopentyl                                                                           2-Cl, 4-phenoxy                                               4-(4-isopropoxyphenoxy)                                                                       4-CH.sub.2 C.sub.6 H.sub.5                                    4-(3-isopropoxyphenoxy)                                                                       3-CH.sub.2 C.sub.6 H.sub.5                                    4-(4-ethoxyphenoxy)                                                                           4-(3-chloro-5-trifluoromethyl-                                                2-pyridyloxy)                                                 4-(3-ethoxyphenoxy)                                                                           4-(3-bromo-5-trifluoromethyl-                                                 2-pyridyloxy)                                                 4-(4-n-propoxyphenoxy)                                                                        4-(3-5-bistrifluoromethyl-2-pyridyloxy)                       4-(4-methoxyphenoxy)                                                                          2-methyl-4-(3,3-dichloro-2-allyloxy)                          4-(3-methoxyphenoxy)                                                                          2-methyl-4-(3,3-dibromo-2-allyloxy)                           4-(3-n-propoxyphenoxy)                                                                        2-CH.sub.3, 3,4-ethylenedioxy                                 2-Cl, 3,4-ethylenedioxy                                                                       4-(4-trifluoromethoxyphenoxy)                                 4-(3-trifluoromethoxyphenoxy)                                                 4-OCH.sub.2 CCH                                                               4-OCH.sub.2 CCBr                                                              4-OCH.sub.2 CCCl                                                              3-OCH.sub.2 CCH                                                               3-OCH.sub.2 CCCl                                                              3-OCH.sub.2 CCBr                                                              ______________________________________                                    

The compounds of the following formulae VII-1 to 18 are shown in Table2.

                  TABLE 2                                                         ______________________________________                                         ##STR14##                                                                     ##STR15##                                                                     ##STR16##                                                                     ##STR17##                                                                     ##STR18##                                                                     ##STR19##                                                                     ##STR20##                                                                     ##STR21##                                                                     ##STR22##                                                                     ##STR23##                                                                     ##STR24##                                                                     ##STR25##                                                                     ##STR26##                                                                     ##STR27##                                                                     ##STR28##                                                                     ##STR29##                                                                     ##STR30##                                                                     ##STR31##                                                                    ______________________________________                                        (R.sup.1).sub.l      (R.sup.1).sub.l                                          ______________________________________                                        4-Cl                 2,4-F.sub.2                                              3-Br                 4-F                                                      3,5-Cl.sub.2         3-Cl                                                     3,5-F.sub.2          3-F                                                      3,4-Cl.sub.2         4-Br                                                     2,4-Cl.sub.2         3,5-Br.sub.2                                             3-I                  2-Cl, 4-OC.sub.2 H.sub.5                                 4-I                  2-Cl, 4-OCH(CH.sub.3).sub.2                              3-C(CH.sub.3).sub.3  3,5-(OC.sub.2 H.sub.5).sub.2                             4-C(CH.sub.3).sub.3  3,5-(OCH(CH.sub.3).sub.2).sub.2                          3-CF.sub.3           3-CH.sub.3, 5-OCH(CH.sub.3).sub.2                        4-CF.sub.3           3-OCF.sub.3                                              3,5-(CF.sub.3).sub.2 4-OCF.sub.3                                              2,4-(CF.sub.3).sub.2 3-OCH.sub.2 CF.sub.3                                     2-Cl, 4-CF.sub.3     4-OCH.sub.2 CF.sub.3                                     2,6-Cl.sub.2, 4-CF.sub.3                                                                           3-SCH.sub.2 CF.sub.3                                     2-Br, 4-CF.sub.3     4-SCH.sub.2 CF.sub.3                                     2-F, 6-Cl, 4-CF.sub.3                                                                              3-Br, 4-OCH.sub.2 CHC(Br).sub.2                          2,6-F.sub.2, 4-CF.sub.3                                                                            3-Br, 4-OCH.sub.2 CHC(Cl).sub.2                          3-OCH.sub.3          3-CH.sub.3                                               4-OCH.sub.3          4-CH.sub.3                                               3-OC.sub.2 H.sub.5   3-cyclopentyl                                            4-OC.sub.2 H.sub.5   4-cycIopentyl                                            3-OCH(CH.sub.3).sub.2                                                                              3-cyclohexyl                                             4-OCH(CH.sub.3).sub.2                                                                              4-cyclohexyl                                             3-OC(CH.sub.3).sub.3 3-phenyl                                                 4-OC(CH.sub.3).sub.3 4-phenyl                                                 3,5-(OCH.sub.3).sub.2                                                                              3-O-cyclopentyl                                          3,4-(OCH.sub.3).sub.2                                                                              4-O-cycIopentyl                                          2-Cl, 4-OCH.sub.3    3-O-cyclohexyl                                           4-O-cyclohexyl       2-Br, 4-OC.sub.2 H.sub.5                                 3-phenoxy            2-Br, 4-OCH(CH.sub.3).sub.2                              4-phenoxy            2-Cl, 4-OCF.sub.3                                        2-Br, 4-OCH.sub.3    2-Br, 4-OCF.sub.3                                        2,4-(NO.sub.2).sub.2                                                          4-CN                                                                          2,6-Cl.sub.2, 4-CF.sub.3                                                      2-F, 6-Cl, 4-CF.sub.3                                                         2,6-F.sub.2, 4-CF.sub.3                                                       2-F, 4-NO.sub.2                                                               2-Cl, 4-NO.sub.2                                                              2-NO.sub.2, 4-CF.sub.3                                                        2,4-(NO.sub.2).sub.2, 6-CF.sub.3                                              2-CF.sub.3, 4-NO.sub.2                                                        4-NHCOCH.sub.3                                                                4-NHCOCF.sub.3                                                                4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)                                   ______________________________________                                    

The compounds of the following formulae VIII-1 to 16 are shown in theTable 3.

                  TABLE 3                                                         ______________________________________                                         ##STR32##                                                                     ##STR33##                                                                     ##STR34##                                                                     ##STR35##                                                                     ##STR36##                                                                     ##STR37##                                                                     ##STR38##                                                                     ##STR39##                                                                     ##STR40##                                                                     ##STR41##                                                                     ##STR42##                                                                     ##STR43##                                                                     ##STR44##                                                                     ##STR45##                                                                     ##STR46##                                                                     ##STR47##                                                                    ______________________________________                                        (R.sup.1).sub.l    (R.sup.1).sub.l                                            ______________________________________                                        3-Cl               4-OCH(CH.sub.3).sub.2                                      4-Cl               2-Cl, 4-OCH.sub.3                                          3-Br               2-Cl, 4-OC.sub.2 H.sub.5                                   4-Br               2-Cl, 4-OCH.sub.2 CH.sub.2 CH.sub.3                        3-C(CH.sub.3).sub.3                                                                              2-Cl, 4-OCH(CH.sub.3).sub.2                                4-C(CH.sub.3).sub.3                                                                              3,4-(OCH.sub.3).sub.2                                      2-Cl, 4-C(CH.sub.3).sub.3                                                                        3,5-(OCH.sub.3).sub.2                                      2-Br, 4-C(CH.sub.3).sub.3                                                                        3-OCF.sub.3                                                3-CF.sub.3         4-OCF.sub.3                                                4-CF.sub.3         3-OCH.sub.2 CF.sub.3                                       3,5-(CH.sub.3).sub.2                                                                             4-OCH.sub.2 CF.sub.3                                       2,4-(CH.sub.3).sub.2                                                                             2-Cl, 4-OCF.sub.3                                          2-F, 4-CF.sub.3    2-Cl, 4-OCH.sub.2 CF.sub.3                                 2-Cl, 4-CF.sub.3   3-SCH.sub.2 CF.sub.3                                       2,6-Cl.sub.2, 4-CF.sub.3                                                                         4-SCH.sub.2 CF.sub.3                                       2-F, 6-Cl, 4-CF.sub.3                                                                            4-OCH.sub.2 CHCH(Cl)                                       2,6-F.sub.2, 4-CF.sub.3                                                                          4-CH.sub.2 (OH)CH.sub.2 CH.sub.3                           3-OCH.sub.3        3-cyclopentyl                                              4-OCH.sub.3        3-O-cyclopentyl                                            3-OC.sub.2 H.sub.5 4-O-cyclopentyl                                            4-OC.sub.2 H.sub.5 4-O-cyclopentyl                                            3-OCH.sub.2 CH.sub.2 CH.sub.3                                                                    3-cyclohexyl                                               4-OCH.sub.2 CH.sub.2 CH.sub.3                                                                    3-O-cyclohexyl                                             3-OCH(CH.sub.3).sub.2                                                                            4-cyclohexyl                                               4-O-cyclohexyl     3-phenoxy                                                  3-phenyl           4-phenoxy                                                  4-phenyl                                                                      ______________________________________                                    

The compounds of the following formulae IX-1 to 54 are shown in Table 4.

                  TABLE 4                                                         ______________________________________                                         ##STR48##                                                                     ##STR49##                                                                     ##STR50##                                                                     ##STR51##                                                                     ##STR52##                                                                     ##STR53##                                                                     ##STR54##                                                                     ##STR55##                                                                     ##STR56##                                                                     ##STR57##                                                                     ##STR58##                                                                     ##STR59##                                                                     ##STR60##                                                                     ##STR61##                                                                     ##STR62##                                                                     ##STR63##                                                                     ##STR64##                                                                     ##STR65##                                                                     ##STR66##                                                                     ##STR67##                                                                     ##STR68##                                                                     ##STR69##                                                                     ##STR70##                                                                     ##STR71##                                                                     ##STR72##                                                                     ##STR73##                                                                     ##STR74##                                                                     ##STR75##                                                                     ##STR76##                                                                     ##STR77##                                                                     ##STR78##                                                                     ##STR79##                                                                     ##STR80##                                                                     ##STR81##                                                                     ##STR82##                                                                     ##STR83##                                                                     ##STR84##                                                                     ##STR85##                                                                     ##STR86##                                                                     ##STR87##                                                                     ##STR88##                                                                     ##STR89##                                                                     ##STR90##                                                                     ##STR91##                                                                     ##STR92##                                                                     ##STR93##                                                                     ##STR94##                                                                     ##STR95##                                                                     ##STR96##                                                                     ##STR97##                                                                     ##STR98##                                                                     ##STR99##                                                                     ##STR100##                                                                    ##STR101##                                                                   ______________________________________                                        (R.sup.1).sub.l      (R.sup.1).sub.l                                          ______________________________________                                        3-C(CH.sub.3).sub.3  2-Cl, 4-OCH(CH.sub.3).sub.2                              4-C(CH.sub.3).sub.3  3-OCF.sub.3                                              3-CF.sub.3           4-OCF.sub.3                                              4-CF.sub.3           2-Cl, 4-OCF.sub.3                                        2-F, 4-CF.sub.3      3-cyclopentyl                                            2-Cl, 4-CF.sub.3     4-cyclopentyl                                            2-F, 6-Cl, 4-CF.sub.3                                                                              3-cyclohexyl                                             2,6-F.sub.2, 4-CF.sub.3                                                                            4-cyclohexyl                                             2,6-Cl.sub.2, 4-CF.sub.3                                                                           3-phenyl                                                 3-OCH.sub.3          4-phenyl                                                 3-OC.sub.2 H.sub.5   3-phenoxy                                                3-OCH(CH.sub.3).sub.2                                                                              4-phenoxy                                                4-OCH.sub.3          3-O-cyclopentyl                                          4-OC.sub.2 H.sub.5   3-O-cyclohexyl                                           4-OCH(CH.sub.3).sub.2                                                                              4-O-cyclohexyl                                           2-Cl, 4-OCH.sub.3    4-O-cyclopentyl                                          2-Cl, 4-OC.sub.2 H.sub.5                                                                           4-Cl                                                     2-CH.sub.3, 3,4-ethylenedioxy                                                 4-OCH.sub.2 CF.sub.3                                                          4-NO.sub.2                                                                    ______________________________________                                    

The compounds of the formulae X-1 to 60 are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                         ##STR102##                                                                    ##STR103##                                                                    ##STR104##                                                                    ##STR105##                                                                    ##STR106##                                                                    ##STR107##                                                                    ##STR108##                                                                    ##STR109##                                                                    ##STR110##                                                                    ##STR111##                                                                    ##STR112##                                                                    ##STR113##                                                                    ##STR114##                                                                    ##STR115##                                                                    ##STR116##                                                                    ##STR117##                                                                    ##STR118##                                                                    ##STR119##                                                                    ##STR120##                                                                    ##STR121##                                                                    ##STR122##                                                                    ##STR123##                                                                    ##STR124##                                                                    ##STR125##                                                                    ##STR126##                                                                    ##STR127##                                                                    ##STR128##                                                                    ##STR129##                                                                    ##STR130##                                                                    ##STR131##                                                                    ##STR132##                                                                    ##STR133##                                                                    ##STR134##                                                                    ##STR135##                                                                    ##STR136##                                                                    ##STR137##                                                                    ##STR138##                                                                    ##STR139##                                                                    ##STR140##                                                                    ##STR141##                                                                    ##STR142##                                                                    ##STR143##                                                                    ##STR144##                                                                    ##STR145##                                                                    ##STR146##                                                                    ##STR147##                                                                    ##STR148##                                                                    ##STR149##                                                                    ##STR150##                                                                    ##STR151##                                                                    ##STR152##                                                                    ##STR153##                                                                    ##STR154##                                                                    ##STR155##                                                                    ##STR156##                                                                    ##STR157##                                                                    ##STR158##                                                                    ##STR159##                                                                    ##STR160##                                                                    ##STR161##                                                                   ______________________________________                                        (R.sup.1).sub.l       (R.sup.1).sub.l                                         ______________________________________                                        3-cyclohexyl          3-OC.sub.2 H.sub.5                                      4-cyclohexyl          4-OC.sub.2 H.sub.5                                      3-OCH(CH.sub.3).sub.2 3-phenyl                                                4-OCH(CH.sub.3).sub.2 4-phenyl                                                ______________________________________                                    

The compounds of the formulae XI-1 to 2 are shown in Table 6.

                  TABLE 6                                                         ______________________________________                                         ##STR162##                                                                    ##STR163##                                                                   ______________________________________                                        (R.sup.1).sub.l  (R.sup.2).sub.m                                              ______________________________________                                        4-OC.sub.2 H.sub.5                                                                             2-(CH.sub.2).sub.2 CH.sub.3, 5-CH(CH.sub.3).sub.2            4-Cl             2,6-(CH.sub.3).sub.2                                         3-Cl             2,6-(CH(CH.sub.3).sub.2).sub.2                               3-Cl             2-CHF.sub.2                                                  4-OCH(CH.sub.3).sub.2                                                                          2-Br, 6-NO.sub.2                                             4-OCH(CH.sub.3).sub.2                                                                          2-I                                                          4-OCH(CH.sub.3).sub.2                                                                          2-F                                                          ______________________________________                                         The position of R.sup.2 is numbered as shown in the formula XI1.         

The compounds of the formulae XII-1 to 4 are shown in Table 7.

                  TABLE 7                                                         ______________________________________                                         ##STR164##                                                                    ##STR165##                                                                    ##STR166##                                                                    ##STR167##                                                                   ______________________________________                                        (R.sup.1).sub.l     (R.sup.1).sub.l                                           ______________________________________                                        3-Cl                4-CF.sub.3                                                4-Cl                4-SCH.sub.2 CF.sub.3                                      3-Br                3-SCH.sub.2 CF.sub.3                                      4-Br                3-phenyl                                                  3-CF.sub.3          4-phenyl                                                  3-cyclopentyl       4-OCH.sub.2 CF.sub.3                                      4-cyclopentyl       3-cyclohexyl                                              2-Cl, 4-CF.sub.3    4-cyclohexyl                                              3-C(CH.sub.3).sub.3 3-phenoxy                                                 4-C(CH.sub.3).sub.3 4-phenoxy                                                 3-OCH.sub.3         3-O-cyclopentyl                                           4-OCH.sub.3         4-O-cyclopentyl                                           3-OC.sub.2 H.sub.5  3-O-cyclohexyl                                            4-OC.sub.2 H.sub.5  4-O-cyclohexyl                                            3-OCH(CH.sub.3).sub.2                                                                             3-Cl, 5-CF.sub.3                                          4-OCH(CH.sub.3).sub.2                                                                             3-Br, 5-CF.sub.3                                          3-OCF.sub.3         3,5-(CF.sub.3).sub.2                                      4-OCF.sub.3         3,5-(CF.sub.3).sub.2, 6-Cl                                3-OCH.sub.2 CF.sub.3                                                          2-Cl, 4-CF.sub.3                                                              5-CF.sub.3                                                                    ______________________________________                                    

The compounds of the formulae XIII-1 to 16 are shown in Table 8.

                  TABLE 8                                                         ______________________________________                                         ##STR168##                                                                    ##STR169##                                                                    ##STR170##                                                                    ##STR171##                                                                    ##STR172##                                                                    ##STR173##                                                                    ##STR174##                                                                    ##STR175##                                                                    ##STR176##                                                                    ##STR177##                                                                    ##STR178##                                                                    ##STR179##                                                                    ##STR180##                                                                    ##STR181##                                                                    ##STR182##                                                                    ##STR183##                                                                   (R.sup.2).sub.m                                                                              (R.sup.2).sub.m                                                ______________________________________                                        2-CF.sub.3     2-CHF.sub.2                                                    2-CH.sub.2 CH.sub.2 CH.sub.3                                                                 2,5-Cl.sub.2                                                   2-CH(CH.sub.3).sub.2                                                                         3,5-Cl.sub.2                                                   2-Cl           trimethylene at positions 2 and 3                              2-Br           tetramethylene at positions 2 and 3                            ______________________________________                                         The position of R.sup.2 is numbered as shown in the formula XIII1        

The compounds of the formulae XIV-1 to 16 are shown in Table 9.

                  TABLE 9                                                         ______________________________________                                         ##STR184##                                                                    ##STR185##                                                                    ##STR186##                                                                    ##STR187##                                                                    ##STR188##                                                                    ##STR189##                                                                    ##STR190##                                                                    ##STR191##                                                                    ##STR192##                                                                    ##STR193##                                                                    ##STR194##                                                                    ##STR195##                                                                    ##STR196##                                                                    ##STR197##                                                                    ##STR198##                                                                    ##STR199##                                                                   ______________________________________                                        (R.sup.1).sub.l                                                                            (R.sup.1).sub.l                                                  ______________________________________                                        4-Cl         3-OCF.sub.3                                                      2-Cl, 4-CF.sub.3                                                                           4-OCF.sub.3                                                      3-CF.sub.3   3-phenyl                                                         4-CF.sub.3   4-phenyl                                                         2,4-(CF.sub.3).sub.2                                                                       3-cyclopentyl                                                    3-OCH.sub.3  4-cyclopentyl                                                    4-OCH.sub.3  3-cyclohexyl                                                     3-OC.sub.2 H.sub.5                                                                         4-cyclohexyl                                                     4-OC.sub.2 H.sub.5                                                                         4-OCH.sub.2 CHC(Cl).sub.2                                        3-OCH(CH.sub.3).sub.2                                                                      4-OCH.sub.2 CHC(Br).sub.2                                        4-OCH(CH.sub.3).sub.2                                                                      2-CH.sub.3, 4-OCH.sub.2 CHC(Cl).sub.2, 5-C(CH.sub.3).sub.3       ______________________________________                                    

The compounds of the formulae XV-1 to 20 are shown in Table 10.

                                      TABLE 10                                    __________________________________________________________________________     ##STR200##                                                                    ##STR201##                                                                    ##STR202##                                                                    ##STR203##                                                                    ##STR204##                                                                    ##STR205##                                                                    ##STR206##                                                                    ##STR207##                                                                    ##STR208##                                                                    ##STR209##                                                                    ##STR210##                                                                    ##STR211##                                                                    ##STR212##                                                                    ##STR213##                                                                    ##STR214##                                                                    ##STR215##                                                                    ##STR216##                                                                    ##STR217##                                                                    ##STR218##                                                                    ##STR219##                                                                   __________________________________________________________________________             Y               (R.sup.2).sub.m                                      __________________________________________________________________________             CH.sub.2        2-Cl                                                          CH.sub.2        2-Br                                                          CH.sub.2        2-CH.sub.3                                                    CH(CH.sub.3)    2-Cl                                                          CH(CH.sub.3)    2-Br                                                          CH(CH.sub.3)    2-CH.sub.3                                                    C(CH.sub.3).sub.2                                                                             2-Cl                                                          C(CH.sub.3).sub.2                                                                             2-Br                                                          C(CH.sub.3).sub.2                                                                             2-CH.sub.3                                                    CH(C.sub.2 H.sub.5)                                                                           2-Cl                                                          CH(C.sub.2 H.sub.5)                                                                           2-Br                                                          CH(C.sub.2 H.sub.5)                                                                           2-CH.sub.3                                                    C(C.sub.2 H.sub.5).sub.2                                                                      2-Cl                                                          C(C.sub.2 H.sub.5).sub.2                                                                      2-Br                                                          C(C.sub.2 H.sub.5).sub.2                                                                      2-CH.sub.3                                                    C(CH.sub.3)(C.sub.2 H.sub.5)                                                                  2-Cl                                                          C(CH.sub.3)(C.sub.2 H.sub.5)                                                                  2-Br                                                          C(CH.sub.3)(C.sub.2 H.sub.5)                                                                  2-CH.sub.3                                                    C(CF.sub.3)(CF.sub.3)                                                                         2-Cl                                                          C(CF.sub.3)(CF.sub.3)                                                                         2-Br                                                          C(CF.sub.3)(CF.sub.3)                                                                         2-CH.sub.3                                                    C(CF.sub.3)(CF.sub.3)                                                                         2,6-Br.sub.2                                                  CCH.sub.2       2-Cl                                                          CCH.sub.2       2-Br                                                          CCH.sub.2       2-CH.sub.3                                                    C(CH.sub.3).sub.2                                                                             2,5-Cl.sub.2                                                  C(CH.sub.3).sub.2                                                                             2-Br                                                          CH(CH(CH.sub.3).sub.2)                                                                        2-Br                                                 __________________________________________________________________________     The position of R.sup.2 is numbered as shown in the formula XV1          

The compounds of the formulae XVI-1 to 8 are shown in Table 11.

                  TABLE 11                                                        ______________________________________                                         ##STR220##                                                                    ##STR221##                                                                    ##STR222##                                                                    ##STR223##                                                                    ##STR224##                                                                    ##STR225##                                                                    ##STR226##                                                                    ##STR227##                                                                   ______________________________________                                        (R.sup.1).sub.l     (R.sup.1).sub.l                                           ______________________________________                                        3-C(CH.sub.3).sub.3 4-cyclopentyl                                             4-C(CH.sub.3).sub.3 3-phenyl                                                  3-OC.sub.2 H.sub.5  3-cyclopentyl                                             4-OC.sub.2 H.sub.5  4-cyclohexyl                                              3-OCH(CH.sub.3).sub.2                                                                             4-OCF.sub.3                                               4-OCH(CH.sub.3).sub.2                                                                             4-phenyl                                                  3-cyclohexyl        3-OCF.sub.3                                               ______________________________________                                    

The compounds of the formulae XVII-1 to 4 are shown in Table 12.

                  TABLE 12                                                        ______________________________________                                         ##STR228##                                                                    ##STR229##                                                                    ##STR230##                                                                    ##STR231##                                                                   ______________________________________                                        (R.sup.1).sub.l       Y                                                       ______________________________________                                        4-OCH(CH.sub.3).sub.2 C(CH.sub.3).sub.2                                       3-OCH(CH.sub.3).sub.2 C(CH.sub.3).sub.2                                       4-OC.sub.2 H.sub.5    C(CH.sub.3).sub.2                                       3-OC.sub.2 H.sub.5    C(CH.sub.3).sub.2                                       4-OCH(CH.sub.3).sub.2 CH(CH.sub.3)                                            3-OCH(CH.sub.3).sub.2 CH(CH.sub.3)                                            4-OC.sub.2 H.sub.5    CH(CH.sub.3)                                            3-OC.sub.2 H.sub.5    CH(CH.sub.3)                                            ______________________________________                                    

The compounds of the formulae XVIII-1 to 36 are shown in Table 13.

                  TABLE 13                                                        ______________________________________                                         ##STR232##                                                                    ##STR233##                                                                    ##STR234##                                                                    ##STR235##                                                                    ##STR236##                                                                    ##STR237##                                                                    ##STR238##                                                                    ##STR239##                                                                    ##STR240##                                                                    ##STR241##                                                                    ##STR242##                                                                    ##STR243##                                                                    ##STR244##                                                                    ##STR245##                                                                    ##STR246##                                                                    ##STR247##                                                                    ##STR248##                                                                    ##STR249##                                                                    ##STR250##                                                                    ##STR251##                                                                    ##STR252##                                                                    ##STR253##                                                                    ##STR254##                                                                    ##STR255##                                                                    ##STR256##                                                                    ##STR257##                                                                    ##STR258##                                                                    ##STR259##                                                                    ##STR260##                                                                    ##STR261##                                                                    ##STR262##                                                                    ##STR263##                                                                    ##STR264##                                                                    ##STR265##                                                                    ##STR266##                                                                    ##STR267##                                                                   ______________________________________                                        (R.sup.1).sub.l     (R.sup.1).sub.l                                           ______________________________________                                        6-CH.sub.3          5-CH.sub.2 CH.sub.3                                       6-CH.sub.2 CH.sub.3 4-CH.sub.3                                                6-CH.sub.2 CH.sub.2 CH.sub.3                                                                      4-C.sub.2 H.sub.5                                         6-phenyl            4-CH(CH.sub.3).sub.2                                      5-phenyl            4-C(CH.sub.3).sub.3                                       5-CH.sub.3          4-Phenyl                                                  5-CH.sub.3, 6-phenyl                                                                              3,4,5,6-F.sub.4                                           5,6-(CH.sub.3).sub.2                                                                              3,5-Cl.sub.2, 4,6-F.sub.2                                 4,6-(CH.sub.3).sub.2                                                                              3,4,5,6-Cl.sub.4                                          4,5-(CH.sub.3).sub.2                                                                              6-OCH.sub.3                                               3,6-(CH.sub.3).sub.2                                                                              6-OC.sub.2 H.sub.5                                        3,5-(CH.sub.3).sub.2                                                                              6-OCH(CH.sub.3).sub.2                                     6-Cl                4-OCH.sub.3                                               6-Br                4-OC.sub.2 H.sub.5                                        3-Cl                4-OCH(CH.sub.3).sub.2                                     5-Cl                5-OCH.sub.3                                               3-Br                5-OC.sub.2 H.sub.5                                        5-Br                5-OCH(CH.sub.3).sub.2                                     4-Cl                3-Br, 5-CF.sub.3                                          4-Br                3-F, 5-CF.sub.3                                           5-CF.sub.3          3-I, 5-CF.sub.3                                           3,5-Cl.sub.2        3,6-(CF.sub.3).sub.2                                      3,5-(CF.sub.3).sub.2                                                                              3-CF.sub.3, 5-Cl                                          4,5-(CF.sub.3).sub.2                                                                              3-CF.sub.3                                                4,6-(CF.sub.3).sub.2                                                                              3,5-(CF.sub.3).sub.2, 6-Cl                                3-Cl, 5-CF.sub.3    4-CF.sub.3                                                3,5,6-F.sub.3       4-CF.sub.3, 6-Cl                                          3,5,6-F.sub.3, 4-CH.sub.3                                                                         3-CF.sub.3, 6-Cl                                                              5-CF.sub.3, 6-Cl                                                              5-NO.sub.2                                                                    3-Br, 5-NO.sub.2                                          ______________________________________                                    

The compounds of the formulae XIX-1 to 54 are shown in Table 14.

                  TABLE 14                                                        ______________________________________                                         ##STR268##                                                                    ##STR269##                                                                    ##STR270##                                                                    ##STR271##                                                                    ##STR272##                                                                    ##STR273##                                                                    ##STR274##                                                                    ##STR275##                                                                    ##STR276##                                                                    ##STR277##                                                                    ##STR278##                                                                    ##STR279##                                                                    ##STR280##                                                                    ##STR281##                                                                    ##STR282##                                                                    ##STR283##                                                                    ##STR284##                                                                    ##STR285##                                                                    ##STR286##                                                                    ##STR287##                                                                    ##STR288##                                                                    ##STR289##                                                                    ##STR290##                                                                    ##STR291##                                                                    ##STR292##                                                                    ##STR293##                                                                    ##STR294##                                                                    ##STR295##                                                                    ##STR296##                                                                    ##STR297##                                                                    ##STR298##                                                                    ##STR299##                                                                    ##STR300##                                                                    ##STR301##                                                                    ##STR302##                                                                    ##STR303##                                                                    ##STR304##                                                                    ##STR305##                                                                    ##STR306##                                                                    ##STR307##                                                                    ##STR308##                                                                    ##STR309##                                                                    ##STR310##                                                                    ##STR311##                                                                    ##STR312##                                                                    ##STR313##                                                                    ##STR314##                                                                    ##STR315##                                                                    ##STR316##                                                                    ##STR317##                                                                    ##STR318##                                                                    ##STR319##                                                                    ##STR320##                                                                    ##STR321##                                                                   ______________________________________                                        (R.sup.1).sub.l     (R.sup.1).sub.l                                           ______________________________________                                        5-phenyl            4-OCH(CH.sub.3).sub.2                                     5-C.sub.2 H.sub.5   5-OCH.sub.3                                               4-CH(CH.sub.3).sub.2                                                                              5-OC.sub.2 H.sub.5                                        4-phenyl            5-CH(CH.sub.3).sub.2                                      5-CF.sub.3          3-Br, 5-CF.sub.3                                          3,5-(CF.sub.3).sub.2                                                                              3,6-(CF.sub.3).sub.2                                      4,5-(CF.sub.3).sub.2                                                                              3-CF.sub.3, 5-Cl                                          4,6-(CF.sub.3).sub.2                                                                              3-CF.sub.3                                                3-Cl, 5-CF.sub.3    3,5-(CH.sub.3).sub.2, 6-Cl                                6-OCH.sub.3         4-CF.sub.3                                                6-OC.sub.2 H.sub.5  4-CF.sub.3, 6-Cl                                          6-OCH(CH.sub.3).sub.2                                                                             3-CF.sub.3, .6-Cl                                         4-OCH.sub.3         3-CF.sub.3, 6-Cl                                          4-OC.sub.2 H.sub.5  5-CF.sub.3, 6-Cl                                          ______________________________________                                         The position of R.sup.1 is numbered as shown in the formula XIX1.        

The compounds of the formulae XX-1 to 16 are shown in Table 15.

                  TABLE 15                                                        ______________________________________                                         ##STR322##                                                                    ##STR323##                                                                    ##STR324##                                                                    ##STR325##                                                                    ##STR326##                                                                    ##STR327##                                                                    ##STR328##                                                                    ##STR329##                                                                    ##STR330##                                                                    ##STR331##                                                                    ##STR332##                                                                    ##STR333##                                                                    ##STR334##                                                                    ##STR335##                                                                    ##STR336##                                                                    ##STR337##                                                                    ##STR338##                                                                    ##STR339##                                                                    ##STR340##                                                                    ##STR341##                                                                    ##STR342##                                                                    ##STR343##                                                                   ______________________________________                                        (R.sup.1).sub.l     (R.sup.1).sub.l                                           ______________________________________                                        5-phenyl            4-OCH(CH.sub.3).sub.2                                     5-C.sub.2 H.sub.5   5-OCH.sub.3                                               4-CH(CH.sub.3).sub.2                                                                              5-OC.sub.2 H.sub.5                                        4-phenyl            5-CH(CH.sub.3).sub.2                                      5-CF.sub.3          3-Br, 5-CF.sub.3                                          3,5-(CF.sub.3).sub.2                                                                              3,6-(CF.sub.3).sub.2                                      4,5-(CF.sub.3).sub.2                                                                              3-CF.sub.3, 5-Cl                                          4,6-(CF.sub.3).sub.2                                                                              3-CF.sub.3                                                3-Cl, 5-CF.sub.3    3,5-(CF.sub.3).sub.2, 6-Cl                                6-OCH.sub.3         4-CF.sub.3                                                6-OC.sub.2 H.sub.5  4-CF.sub.3, 6-Cl                                          6-OCH(CH.sub.3).sub.2                                                                             3-CF.sub.3, 6-Cl                                          4-OCH.sub.3         5-CF.sub.3, 6-Cl                                          4-OC.sub.2 H.sub.5                                                            ______________________________________                                         The position of R.sup.1 is numbered as shown in the formula XX1.         

The compounds of the formulae XXI-1 to 16 are shown in Table 16.

                  TABLE 16                                                        ______________________________________                                         ##STR344##                                                                    ##STR345##                                                                    ##STR346##                                                                    ##STR347##                                                                    ##STR348##                                                                    ##STR349##                                                                    ##STR350##                                                                    ##STR351##                                                                    ##STR352##                                                                    ##STR353##                                                                    ##STR354##                                                                    ##STR355##                                                                    ##STR356##                                                                    ##STR357##                                                                    ##STR358##                                                                    ##STR359##                                                                   ______________________________________                                        (R.sup.1).sub.l    (R.sup.1).sub.l                                            ______________________________________                                        5-CF.sub.3         3,5-(CF.sub.3).sub.2, 6-Cl                                 3,5-(CF.sub.3).sub.2                                                                             4-CF.sub.3                                                 4,6-(CF.sub.3).sub.2                                                                             4-CF.sub.3, 6-Cl                                           3-Cl, 5-CF.sub.3   3-CF.sub.3, 6-Cl                                           3-Br, 5-CF.sub.3   5-CF.sub.3, 6-Cl                                           3,6-(CF.sub.3).sub.2                                                          ______________________________________                                         The position of R.sup.1 is numbered as shown in the formula XXI1.        

The compounds of the formulae XXII-1 to 14 are shown in Table 17.

                  TABLE 17                                                        ______________________________________                                         ##STR360##                                                                    ##STR361##                                                                    ##STR362##                                                                    ##STR363##                                                                    ##STR364##                                                                    ##STR365##                                                                    ##STR366##                                                                    ##STR367##                                                                    ##STR368##                                                                    ##STR369##                                                                    ##STR370##                                                                    ##STR371##                                                                    ##STR372##                                                                    ##STR373##                                                                   ______________________________________                                        (R.sup.1).sub.l     (R.sup.1).sub.l                                           ______________________________________                                        5-CF.sub.3          3,5-(CF.sub.3).sub.2, 6-Cl                                3,5-(CF.sub.3).sub.2                                                                              4-CF.sub.3                                                4,6-(CF.sub.3).sub.2                                                                              4-CF.sub.3, 6-Cl                                          3-Cl, 5-CF.sub.3    3-CF.sub.3, 6-Cl                                          3-Br, 5-CF.sub.3    5-CF.sub.3, 6-Cl                                          3,6-(CF.sub.3).sub.2                                                          ______________________________________                                         The position of R.sup.1 is numbered as shown in the formula XXII1.       

The compounds of the formulae XXIII-1 to 8 are shown in Table 18.

                  TABLE 18                                                        ______________________________________                                         ##STR374##                                                                    ##STR375##                                                                    ##STR376##                                                                    ##STR377##                                                                    ##STR378##                                                                    ##STR379##                                                                    ##STR380##                                                                    ##STR381##                                                                   ______________________________________                                        (R.sup.1).sub.l      (R.sup.1).sub.l                                          ______________________________________                                        3,5-(CF.sub.3).sub.2 3-Br, 5-CF.sub.3                                         3-Cl, 5-CF.sub.3                                                              ______________________________________                                         The position of R.sup.1 is numbered as shown in the formula XIII1.       

The compounds of the formulae XXIV-1 to 14 are shown in Table 19.

                  TABLE 19                                                        ______________________________________                                         ##STR382##                                                                    ##STR383##                                                                    ##STR384##                                                                    ##STR385##                                                                    ##STR386##                                                                    ##STR387##                                                                    ##STR388##                                                                    ##STR389##                                                                    ##STR390##                                                                    ##STR391##                                                                    ##STR392##                                                                    ##STR393##                                                                    ##STR394##                                                                    ##STR395##                                                                   ______________________________________                                        (R.sup.1).sub.l       (R.sup.1).sub.l                                         ______________________________________                                        3-Cl, 5-CF.sub.3      5-CF.sub.3                                              3-Br, 5-CF.sub.3      5-phenyl                                                3,5-(CF.sub.3).sub.2  4-phenyl                                                3,5-(CF.sub.3).sub.2, 6-Cl                                                                          6-phenyl                                                ______________________________________                                         The position of R.sup.1 is numbered as shown in the formula XXIV1.       

The compounds of the formulae XXV-1 to 8 are shown in Table 20.

                  TABLE 20                                                        ______________________________________                                         ##STR396##                                                                    ##STR397##                                                                    ##STR398##                                                                    ##STR399##                                                                    ##STR400##                                                                    ##STR401##                                                                    ##STR402##                                                                    ##STR403##                                                                   ______________________________________                                        (R.sup.1).sub.l    (R.sup.1).sub.l                                            ______________________________________                                        5-CF.sub.3         5-phenyl                                                   3-Cl, 5-CF.sub.3   4-cyclohexyl                                               3-Br, 5-CF.sub.3   5-cyclohexyl                                               3,5-(CF.sub.3).sub.2                                                                             3,5-(CF.sub.3).sub.2, 6-Cl                                 4-phenyl                                                                      ______________________________________                                         The position of R.sup.1 is numbered as shown in the formula XXVI.        

The compounds of the formulae XXVI-1 to 8 are shown in Table 21.

                  TABLE 21                                                        ______________________________________                                         ##STR404##                                                                    ##STR405##                                                                    ##STR406##                                                                    ##STR407##                                                                    ##STR408##                                                                    ##STR409##                                                                    ##STR410##                                                                    ##STR411##                                                                   (R.sup.1).sub.l      (R.sup.1).sub.l                                          ______________________________________                                        4-OCH.sub.3          4-OCH.sub.2 CF.sub.3                                     3-OCH.sub.3          3-cyclohexyl                                             4-OC.sub.2 H.sub.5   4-cyclohexyl                                             3-OC.sub.2 H.sub.5   3-cyclopentyl                                            4-OCH(CH.sub.3).sub.2                                                                              4-cyclopentyl                                            3-OCH(CH.sub.3).sub.2                                                                              3-phenoxy                                                3-OCF.sub.3          4-phenoxy                                                4-OCF.sub.3          3-phenyl                                                 3-OCH.sub.2 CF.sub.3 4-phenyl                                                 ______________________________________                                    

The intermediate compound II of the present invention can be produced,for example, by the methods of schemes 1 to 10. ##STR412##

The intermediate aldehyde compound of the formula V of the presentinvention can be produced by the following scheme: ##STR413##

The intermediate compound represented by the formula III and the alcoholcompound represented by the formula IV can be produced by the scheme 11below or commercially available. ##STR414##

The dihalopropene compound of the present invention is effective forcontrolling noxious insects, mites and nematodes listed below:

Hemiptera

Delphacidae (planthoppers) such as Laodelphax striatellus, Nilaparvatalugens and Sogatella furcifera; Deitocephalidae (leaf hoppers) such asNephotettix cincticeps and Nephotettix virescens, Aphididae (aphids),Pentatomidae (stink bugs), Aleyrodidae, Coccoidea (scale insects),Tingidae (lacebugs), Psyllidae (jumping plant-lices), etc.;

Lepidoptera

Pyralidae such as Chilo suppressalis, Cnaphalocrocis medinalis, Ostrinianubilalis, Parapediasia teterrella, Notarcha derogata and Plodiainterpunctella, Noctuidae (owlet moths) such as Spodoptera litura,Pseudaletia separata, Mamestra brassicae, Agrotis ipsilon, Heliothismoths, Helicoverpa moths, Pieridae such as Pieris rapae crucivora,Tortricidae (bell moths) such as Grapholita molesta and Cydia pomonella,Carposina niponensis, Lyonetiidae (leaf mining moths), Euproctis andLymantria (gypsy) moths, Yponomeutidae such as Plutella xylostella,Gelechiidae such as Pectinophora gossypiella, Arctiidae such asHyphantria cunea, Tinea translucens, Tineola bisselliella, etc.;

Diptera

Culex (house mosquitos) such as Culex pipiens pallens and Culestritaeniorhynchus, Aedes such as Aedes albopictus and Aedes aegypti,Anophelinae such as Anophelies sinensis, Chironomidae (midges), Muscidaesuch as Musca domestica (house fly) and Muscina stabulans, Calliphoridae(blow flies), Sarcophagidae (flesh flies), Anthomyiidae such as DeliaPlatura and Delia antigua, Trypetidae (fruit flies), Drosophilidae (wineflies), Psychodidae (moth flies), Tabanidae (deer flies), Simuliidae(black flies), Stomoxyinae, Agromyzidae (leaf miner flies) etc.;

Coleoptera (beetles)

Diabrotica (corn rootworms) such as Diabrotica virgifera and Diabroticaundecimpunctata, Scarabaeidae such as Anomala cuprea and Anomalarufocuprea, Curculionidae (snout beetles) such as Sitophilus zeamais(grain weevils), Lissorhoptrus oryzophilus, Hypera postica, andCallosobruchus chinesis, Neatus ventralis (darkling beetles) such asTenebrio molitor and Tribolium castaneum, Chrysomelidae (leaf beetles)such as Aulacophora femoralis, and Phyllotreta striolata, Anobiidae(death-watch beetles), Epilachna spp. such as Epilachnavigintioctopunctata, Lyctidae (powder-post beetles), Bostrychidae(lesser grain borers), Cerambycidae, etc.;

Blattaria (cockroaches)

Blattella germanica (croton bugs), Periplaneta fuliginosa, Periplanetaamericana, Periplaneta brunnea, Blatta orientalis, etc.;

Thysanoptera (thrips)

Thrips palmi, Thrips tabaci, Thrips hawaiiensis, etc.;

Hymenoptera

Formicidae (ants), Vespa (hornets), Bethylidae (bethylid wasps),Tenthredinoidae (sawflies) such as Athalia rosae japonensis (cabbagesawfly), etc.;

Orthoptera

Gryllotalpha (mole crickets), Acridoidea (grasshoppers), etc.;

Siphonaptera (fleas)

Purex irritans, etc.;

Anoplura (sucking louses)

Pediculus humanus capitis, Phthirus pubis, etc.;

Isoptera (termites)

Reticulitermes speratus, Coptotermes formosanus, etc.;

Mites

Tetranychidae (spider mites) such as Tetranychus cinnabarinus,Tetranychus urticae, Tetranychus kanzawai, Panonychus citri andPanonychus ulmi, Eriophyidae such as Aculops pelekassi and Calacaruscarinatus, Tarsonemidae such as Polyphaqotarsonemus latus,Tenuipalpidae, Tuckerellidae, Ixodidae (ticks) such as Boophilusmicroplus, Acaridae, Pyroglyphidae, Cheyletidae, Dermanyssidae, etc.;

Moreover, the dihalopropene compounds of the present invention are alsoeffective for controlling various insects with increased resistance tocommercially available insecticides.

For the practical use of the dihalopropene compound of the presentinvention as an active ingredient of insecticides, acaricide ornematocides, it may be used as such; however, the dihalopropene compoundof the present invention is usually formulated into oil sprays,emulsifiable concentrates, wettable powders, flowable concentrates suchas water suspensions or emulsions, granules, dusts, aerosols, heatingfumigants such as combustible fumigant, chemical fumigant and porousceramics fumigant, ULV formulations and poison baits. These formulationsare usually prepared by mixing the dihalopropene compound of the presentinvention with a solid carrier, a liquid career, a gaseous carrier orbait, and a surfactant and any other auxiliary for formulation are addedthereto, if necessary. These formulations usually contain thedihalopropene compound of the present invention as an active ingredientin an mount of 0.01% to 95% by weight.

Examples of the solid carrier to be used for the formulation are finepowder or granules of clays such as kaolin clay, diatomaceous earth,synthetic hydrated silicon oxide, bentonite and acid clay; talc,ceramics, inorganic minerals such as sericite, quartz, sulfur, activecarbon, calcium carbonate and hydrated silica; and chemical fertilizerssuch as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea andammonium chloride. Examples of the liquid carrier are water; alcoholssuch as methanol and ethanol; ketones such as acetone and methylethylketone; aromatic hydrocarbons such as benzene, toluene, xylene,ethylbenzene and methylnaphthalene; aliphatic hydrocarbons such ashexane, cyclohexane, kerosine and gas oil; esters such as ethyl acetateand butyl acetate; nitriles such as acetonitrile and isobutyronitrile;ethers such as diisopropyl ether and dioxane; acid amides such asN,N-dimethylformamide and N,N-dimethylacetamide; halogenatedhydrocarbons such as dichloromethane, trichloroethane and carbontetrachloride; dimethyl sulfoxide; and vegetable oils such as soybeanoil and cottonseed oil. Examples of the gaseous carrier or propellantare CFCs (chlorofluorocarbons), butane gas, LPG (liquefied petroleumgas), diethyl ether and carbon dioxide.

Examples of the surfactant are alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, alkyl aryl ethers, polyethylene glycols, polyethyleneglycol ethers, polyhydric alcohol derivatives and sugar alcoholderivatives.

Examples of the auxiliary for the formulation, such as a fixing agent ora dispersing agent, are casein, gelatin, polysaccharides such as starch,gum arabic, cellulose derivatives and alginic acid, lignin derivatives,bentonite, sugars and synthetic water-soluble polymers such as polyvinylalcohol, polyvinyl pyrrolidone and polyacrylic acid. Examples of thestabilizer are PAP (isopropyl acid phosphate), BHT(2,6-di-t-butyl-4-methylphenol), BHA (mixture of2-t-butyl-4-methoxyphenol and 3-t-butyl-4-methoxyphenol), vegetableoils, mineral oils, surfactants, fatty acids and esters of fatty acids.

Examples of the base material to be used in the combustible fumigant areexothermic agents such as nitrates, nitrites, guanidine salts, potassiumchlorate, nitrocellulose, ethylcellulose or wood powder; pyrolyticstimulating agents such as alkaline metal salts, alkaline earth metalsalts, dichromates or chromates; oxygen sources such as potassiumnitrates; combustion assistants such as melamine or wheat starch; bulkfillers such as diatomaceous earth; and binding agents such as syntheticglue.

Examples of the base material to be used in the chemical fumigant areexothermic agents such as alkaline metal sulfides, polysulfides,hydrogensulfides, hydrated salts or calcium oxide; catalytic agents suchas carbonaceous substances, iron carbide or active clay; organic foamingagents such as azodicarbonamide, benzenesulfonylhydrazide,N,N'-dinitrosopentamethylenetetramine, polystyrene or polyurethane; andfillers such as natural and synthetic fibers.

Examples of the base material to be used in the poison baits are baitmaterials such as grain powder, purified vegetable oil, sulfur orcrystalline cellulose; antioxidants such as dibutylhydroxytoluene ornordihydroguaiaretic acid; preservatives such as dehydroacetic acid;substances for preventing erroneous eating, such as red pepper powder;attractant flavors such as cheese flavor or onion flavor.

The flowable concentrates such as water suspensions and emulsions areusually obtained by finely dispersing the dihalopropene compound of thepresent invention at a ratio of 1% to 75% in water containing a 0.5% to15% dispersing agent, a 0.1% to 10% suspension assistant (e.g.,protective colloid or a thixotropy-giving compound) and 0% to 10%additives (e.g., antifoamers, stabilizers, bactericides, rust preventiveagents, antimolds, developing agents, penetrating assistants and antifreezing agents).

The dihalopropene compound of the present invention may be dispersed inoil having substantially no solubility thereof, to form oil suspensions.Examples of the protective colloid are casein, gelatin, gums, celluloseethers and polyvinyl alcohol. Examples of the thixotropy-giving compoundare bentonite, aluminum magnesium silicate, xanthan gum or polyacrylicacid.

The formulation thus obtained is used as such or after dilution withwater. The formulations of the present invention may be used togetherwith other insecticides, acaricides, nematocides, bactericides,herbicides, plant growth regulators, synergists, fertilizers and/or soilconditioners under non-mixing conditions or pre-mixing conditions.

Examples of the insecticide, acaricide and/or nematocide to be used areorganophosphorous compounds such as Fenitrothion (O,O-dimethylO-(3-methyl-4-nitrophenyl)phosphorothionate!, Fenthion O,O-dimethylO-(3-methyl-4-methylthiophenyl)phosphorothionate!, Diazinon (Dimpylate)O,O-diethyl-O-2-isopropyl-6-methylpyrimidin-4-ylphosphorothioate!,Chlorpyriphos O,O-diethyl-O-3,5,6-trichloro-2-pyridylphosphorothioate!,Acephate O,S-dimethyl acetylphosphoramidothioate!, Methidachion (DMTP)S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethylO,O-dimethylphosphorothiolothionate!, Disulfoton O,O-diethylS-2-ethylthioethyl phosphorothiolothionate!, Dichlorvos (DDVP)2,2-dichlorovinyl dimethyl phosphate!, Sulprofos O-ethylO-4-methylthiophenyl S-propyl phosphorodithioate!, CyanophosO-4-cyanophenyl-O,O-dimethylphosphorothioate!, Dioxabenzofos2-methoxy-4H-1,3,2-benzodioxaphosphorin-2-sulfide!, DimethoateO,O-dimethyl S-(N-methyl-carbamoylmethyl)phosphorodithioate!, Phenthoateethyl 2-dimethoxyphosphinothiaylthiophenylacetate!, Malathion1,2-bis(ethoxylcarbonyl)-ethyl O,O-dimethyl phosphorothiolothionate!,Trichlorfon (Metrifonate) dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate!, Azinphos-methylS-(3,4-dihydro-4-oxo-1,2,3-benzotriazine-3-ylmethyl) dimethylphosphorothiolothionate!, Monocrotophosdimethyl-(E)-1-methyl-2-(methylcarbamoyl)vinyl phospahte!and EthionO,O,O',O'-tetraethyl-S,S'-methylenebis(phosphorothiolothionate)!.

Other examples are carbamate compounds such as BPMC 2-sec-butylphenylmethyl carbamate!, Benfuracarb ethyl N-(2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl(methyl)aminothio)-N-isopropyl-β-alaninate!,Propoxur(PHC) 2-isopropoxyphenyl N-methyl carbamate!, Carbosulfan2,3-dihydro-2,2-dimethyl-7-benzo b!furanyl N-dibutylaminothio-N-methylcarbamate!, Carbaril 1-naphthyl N-methylcarbamate!, MethomylS-methyl-N-((methylcarbamoyl)oxy)thioacetoimidate!, Ethiofencarb2-(ethylthiomethyl)phenyl methylcarbamate!, Aldicarb2-methyl-2-(methylthio)propionaldehyde O-(methylcarbamoyl)oxime!, OxamylN,N-dimethyl 2-methylcarbamoyloxyimino-2-(methylthio)acetamide! andFenothiocarb S-(4-phenoxybutyl)-N,N-dimethyl thiocarbamate!.

Other examples are pyrethroid compounds such as Etofenprox2-(4-ethoxyphenyl)-2-methylpropyl-3-phenoxybenzyl ether!, Fenvalerate(RS)-α-cyano-3-phenoxybenzyl-(RS)-2-(4-chlorophenyl)-3-methylbutyrate!,S-Fenvalerate (S)-α-cyano-3-phenoxybenzyl(S)-2-(4-chlorophenyl)-3-methylbutyrate!, Fenpropathrin(RS)-α-cyano-3-phenoxybenzyl2,2,3,3-tetramethylcyclopropanecarboxylate!, Cypermethrin(RS)-α-cyano-3-phenoxybenzyl(1RS,3RS)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate!,Permethrin 3-phenoxybenzyl(1RS,3RS)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate!,Cyhalothrin (RS)-α-cyano-3-phenoxybenzyl(Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoropropen-1-yl)-2,2-dimethylcyclopropanecarboxylate!, Deltamethrin(S)-α-cyano-3-phenoxybenzyl(1R,3R)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate!,Cycloprothrin (RS)-α-cyano-3-phenoxybenzyl(RS)-2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylate!,Fluvalinate α-cyano-3-phenoxybenzylN-(2-chloro-α,α,α-trifluoro-p-tolyl)-D-valinate!, Bifenthrin2-methylbiphenyl-3-ylmethyl)(Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoropropen-1-yl)-2,2-dimethylcyclopropanecarboxylate!,Acrinathrin (S)-(α)-cyano-(3-phenoxyphenyl)methyl(1R)-(1α(S*),3α(Z))-2,2-dimethyl-3-(3-oxo-3-(2,2,2-trifluoro-1-(trifluoromethyl)ethoxy-1-propenyl)cyclopropanecarboxylate!,2-methyl-2-(4-bromodifluoromethoxyphenyl)propyl (3-phenoxybenzyl)ether,Traromethrin (S)-α-cyano-3-phenoxylbenzyl(1R,3S)-3-((1'RS)(1',1',2',2'-tetrabromoethyl))-2,2-dimethylcyclopropanecarboxylate!and Silafluofen4-ethoxylphenyl(3-(4-fluoro-3-phenoxyphenyl)propyl)dimethylsilane!.

Other examples are thiadiazine derivatives such as Buprofezin2-t-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiazin-4-one!,nitroimidazolidine derivatives such as Imidacloprid1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylidenamine!,Nereistoxin derivatives such as CartapS,S'-(2-dimethylaminotrimethylene)bisthiocarbamate!, ThiocyclamN,N-dimethyl-1,2,3-trithian-5-ylamine! and BensultapS,S'-2-dimethylaminotrimethylene di(benzenethiosulfonate)!,N-cyanoamidine derivatives such asN-cyano-N'-methyl-N'-(6-chloro-3-pyridylmethyl)acetoamidine, chlorinatedhydrocarbons such as Endosulfan6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methanobenzoe!-2,4,3-dioxathiepin 3-oxide!, γ-BHC1,2,3,4,5,6-hexachlorocyclohexane!,1,1-bis(chlorophenyl)-2,2,2-trichloroethanol, benzoylphenylureacompounds such as Chlorofluazuron1-(3,5-dichloro-4-(3-chloro-5-trifluoromethylpyrid-2-yloxy)phenyl)-3-(2,6-difluorobenzoyl)urea!,TeflubenzuronI-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea! andFulphenoxron1-(4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl)-3-(2,6-difluorobenzoyl)urea!,formamidine derivatives such as AmitrazN'-(2,4-dimethylphenyl)-N-((2,4-dimethylphenyl)imino)methyl)-N-methylmethanimidamide!and ChlordimeformN'-(4-chloro-2-methylphenyl)-N,N-dimethylmethanimidamide!, thioureaderivatives such as DiafenthiuronN-(2,6-diisopropyl-4-phenoxyphenyl)-N'-t-butylthiourea!; Fipronyl(5-amino-1-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)-4-trifluoromethylsulfinylpyrazole-3-carbonitrite,Bromopropylate isopropyl 4,4'-dibromobenzilate!, Tetradifon2,4,4',5-tetrachlorodiphenyl sulfone!, Quinomethionate6-methyl-2-oxo-1,3-dithiolo-(4,5-b)quinoxaline!, Propargite2-(4-(1,1-dimethylethyl)phenoxy)cyclohexyl-2-propynyl sulfite!,Fenbutatin oxide bis(tris(2-methyl-2-phenylpropyl)tin)oxide!,Hexythiazox(4RS,5RS)-5-(4-chlorophenyl)-N-chlorohexyl-4-methyl-2-oxo-1,3-thiazolidine-3-carboxamide!,Chlofentezine 3,6-bis(2-chlorophenyl)-1,2,4,5-tetrazine!, Pyridathioben2-t-butyl-5-(4-t-butylbenzylthio)-4-chloropyridazin-3(2H)-one!,Phenpyroxymatet-butyl(E)-4-((1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl)benzoate!,Debphenpyrad N-4-t-butylbenzyl)-4-chloro-3-ethyl-1-methyl-5-pyrazolcarboxamide!, polynactin complexes including tetranactin, trinactin anddinactin; Milbemectin, Avermectin, Ivermectin, Azadilactin AZAD! andPyrimidifen5-chloro-N-(2-(4-(2-ethoxyethyl)-2,3-dimethylphenoxy)ethyl)-6-ethylpyrimidine-4-amine!.

When the dihalopropene compound of the present invention is applied asan active ingredient of insecticides, nematocides or acaricides foragricultural use, the amount for application is usually 0.1 to 100 g ormore, preferably 10 to 100 g per 1000 m². When emulsifiableconcentrates, wettable powders or flowable concentrates of the presentcompound are diluted with water, the concentration for application is0.1 to 500 ppm. Granules and dusts are used without any dilution. Whenthe dihalopropene compound of the present invention is applied as anactive ingredient of insecticides or acaricides for domestic use, theemulsifiable concentrates, wettable powders, flowable concentrates andemulsifiable concentrates are diluted, for example, with water to aconcentration of 0.1 to 500 ppm. Oil sprays, aerosols, fumigants, ULVagents and poisonous baits are used without any dilution,

The amount and concentration for application may be changed optionallyaccording to the type of the formulation used, time, place and method ofapplication, the type of noxious organisms and the damage.

The present invention will be further illustrated by the followingExamples, Formulation Examples and Biological Test Examples, which arenot to be construed to limit thereof.

The following will describe some examples of the dihalopropene compoundof the present invention.

EXAMPLE 1

Production of compound 208 by production process A

To a mixture of 93 mg of3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenol, 40 mg ofpotassium carbonate and 10 ml of N,N-dimethylformamide, a solutionprepared by dissolving 42 mg of 1,1,3-trichloro-1-propene in 3 ml ofN,N-dimethylformamide was added dropwise at room temperature withstirring. After stirring at room temperature for 5 hours, the reactionsolution was poured into ice-water, and extracted twice with 40 ml ofdiethyl ether. Then, the ether layers were combined, washed with water,dried over anhydrous magnesium sulfate and concentrated to give a crudeproduct. This crude product was subjected to silica gel chromatographyto give 96 mg of3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,yield 79%; m.p., 97.8° C.

EXAMPLE 2

Production of compound 1 by production process A

To a mixture of 0.65 g of 3-ethyl-4-(4-isopropoxyphenoxy)phenol, 0.35 gof potassium carbonate and 10 ml of N,N-dimethylformamide, a solutionprepared by dissolving 0.73 g of 1,1,3-tribromo-1-propene in 5 ml ofN,N-dimethylformamide was added dropwise at room temperature withstirring. After stirring at room temperature for 12 hours, the reactionsolution was poured into ice-water, and extracted twice with 50 ml ofdiethyl ether. Then, the ether layers were combined, washed with water,dried over anhydrous magnesium sulfate and then concentrated to give acrude product. This crude product was subjected to silica gelchromatography to give 0.80 g of3-ethyl-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,yield 71%: n_(D) ²³.0 1.5761.

EXAMPLE 3

Production of compound 130 by production process A

To a solution prepared by dissolving 0.44 g of2-trifluoromethyl-4-(3-ethoxyphenoxy)phenol in 10 ml ofN,N-dimethylformamide, 0.062 g of sodium hydride (60% oil-based) wasadded with stirring under ice cooling. After 10 minutes, a solutionprepared by dissolving 0.24 g of 1,1,3-trichloro-1-propene in 5 ml ofN,N-dimethylformamide was added dropwise under ice cooling. Afterstirring at room temperature for 10 hours, the reaction solution waspoured into ice-water, and extracted twice with 50 ml of diethyl ether.Then, the ether layers were combined, washed with water, dried overanhydrous magnesium sulfate and concentrated to give a crude product.This crude product was subjected to silica gel chromatography to give0.37 g of2-trifluoromethyl-4-(3-ethoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,yield 62%; n_(D) ²³.6 1.5369.

EXAMPLE 4

Production of compound 206 by production process A

To a mixture of 0.77 g of2,5-dichloro-4-(3-bromo-5-trifluoromethyl-2-pyridyloxy)phenol, 0.29 g ofpotassium carbonate and 20 ml of N,N-dimethylformamide, a solutionprepared by dissolving 0.31 g of 1,1,3-trichloropropene in 5 ml ofN,N-dimethylformamide was added dropwise at room temperature withstirring. After stirring at room temperature for 10 hours, the reactionsolution was poured into ice-water, and extracted twice with 50 ml ofethyl acetate. Then, the ethyl acetate layers were combined, washed withwater, dried over anhydrous magnesium sulfate and then concentrated togive a crude product. This crude product was subjected to silica gelchromatography to give 0.81 g of2,5-dichloro-4-(3-bromo-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,yield 83%; m.p., 95.4° C.

EXAMPLE 5

Production of compound 273 by production process A

To a mixture of 0.59 g of 2-bromo-4-(4-chlorophenylthio)phenol, 0.28 gof potassium carbonate and 20 ml of N,N-dimethylformamide, a solutionprepared by dissolving 0.30 g of 1,1,3-trichloropropene in 5 ml ofN,N-dimethylformamide was added dropwise at room temperature withstirring. After the mixture was stirred at room temperature for 6 hours,the reaction solution was poured into ice-water, and extracted twicewith 50 ml of diethyl ether. Then, the ether layers were combined,washed with water, dried over anhydrous magnesium sulfate and thenconcentrated to give a crude product. This crude product was subjectedto silica gel column chromatography to give 0.62 g of2-bromo-4-(4-chlorophenylthio)-1-(3,3-dichloro-2-propenyloxy)benzene,yield 78%; n_(D) ²⁵.0 1.6514.

EXAMPLE 6

Production of compound 275 by production process B

To a solution prepared by dissolving 0.65 g of2-bromo-4-(1-methyl-1-(4-ethoxyphenyl))ethylphenol, 0.25 g of3,3-dichloroallyl alcohol and 0.51 g of triphenylphosphine in 10 ml oftetrahydrofuran, a solution prepared by dissolving 0.34 g ofdiethylazodicarboxylate in 5 ml of tetrahydrofuran was added dropwise atroom temperature with stirring. After stirring at room temperature for24 hours, the reaction solution was concentrated to give a residue. Thisresidue was subjected to silica gel chromatography to give 0.28 g of2-bromo-4-(1-methyl-1-(4-ethoxyphenyl))ethyl-1-(3,3-dichloro-2-propenyloxy)benzene,yield 32%; n_(D) ²⁵.0 1.5869.

EXAMPLE 7

Production of compound 196 by production process B

To a solution prepared by dissolving 0.55 g of2-trifluoromethyl-4-(4-ethoxyphenoxy)phenol, 0.40 g of 3,3-dibromoallylalcohol and 0.49 g of triphenylphosphine in 10 ml of tetrahydrofuran, asolution prepared by dissolving 0.38 g of diisopropylazodicarboxylate in5 ml of tetrahydrofuran was added dropwise at room temperature withstirring. After stirring at room temperature for 12 hours, the reactionsolution was concentrated. Then, 20 ml of diethyl ether was addedthereto, and the precipitate was filtered off. The resulting filtratewas concentrated, and subjected to silica gel column chromatography togive 0.30 g of2-trifluoromethyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,yield 32%; n_(D) ²⁴.0 1.5480.

Example 8

Production of compound 68 by production process C

First, 0.38 g of zinc dust, 1.54 g of triphenylphosphine, 1.94 g ofcarbon tetrabromide and 20 ml of methylene chloride were charged into areaction vessel, and stirred at room temperature. After 24 hours, asolution prepared by dissolving 1.0 g of (2-bromo-4-(3-chlorophenoxy)phenoxy)acetaldehyde in 5 ml of methylene chloride was added dropwise tothe solution with stirring. After stirring at room temperature for 6hours, the reaction solution was concentrated to give a residue. Thisresidue was subjected to silica gel column chromatography to give 0.48 gof 2-bromo-4-(3-chlorophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,yield 33%; n_(D) ²⁴.0 1.6282.

EXAMPLE 9

Production of compound 212 by production process A

To a mixture of 0.56 g, of3,5-dichloro-4-(3,5-bistrifluoromethyl-2-pyridyloxy)phenol, 0.22 g ofpotassium carbonate and 20 ml of N,N-dimethylformamide, a solutionprepared by dissolving 0.23 g of 1,1,3-trichloro-1-propene in 5 ml ofN,N-dimethylformamide was added dropwise at room temperature withstirring. After stirring at room temperature for 7 hours, the reactionsolution was poured into ice-water, and extracted twice with 50 ml ofdiethyl ether. Then, the ether layers were combined, washed with water,dried over anhydrous magnesium sulfate and then concentrated to give acrude product. This crude product was subjected to silica gelchromatography to give 0.50 g of3,5-dichloro-4-(3,5-bistrifluoromethyl-2-pyridyloxy)-2-(3,3-dichloro-2-propenyloxy)benzene,yield 70%; m.p., 78.2° C.

EXAMPLE 10

Production of compound 210 by production process A

To a mixture of 0.83 g of3,5-dichloro-4-(3-bromo-5-trifluoromethyl-2-pyridyloxy)phenol, 0.31 g ofpotassium carbonate and 20 ml of N-dimethylformamide, a solutionprepared by dissolving 0.33 g of 1,1,3-trichloro-1-propene in 5 ml ofN,N-dimethylformamide was added dropwise at room temperature withstirring. After stirring at room temperature for 7 hours, the reactionsolution was poured into ice-water, and extracted twice with 50 mi ofdiethyl ether. Then, the ether layers were combined, washed with water,dried over anhydrous magnesium sulfate and then concentrated to give acrude product. This crude product was subjected to silica gelchromatography to give 0.79 g of3,5-dichloro-4-(3-bromo-5-trifluoromethyl-2-pyridyloxy)-2-(3,3-dichloro-2-propenyloxy)benzene,yield 75%; m.p., 90.7° C.

Other examples of the dihalopropene compound of the present inventionwill be described along with their compound numbers.

(1)3-Ethyl-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.5761

(2)2-Isopropyl-4-(3-phenylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵.0 1.6035

(3)2-Isopropyl-4-(3-phenylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵.0 1.6223

(4)2-Isopropyl-4-(2,4-diisopropylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.5 1.5467

(5)2-Isopropyl-4-(2,4-isopropylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.5 1.5646

(6)2-Phenyl-4-(4-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.0 1.5966

(7)2-Phenyl-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.6141

(8)2-Isopropyl-4-(4-phenoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.0 1.5887

(9)2-Isopropyl-4-(4-phenoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.6068

(10)2-Allyl-4-(4-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.0 5638

(11)2-Allyl-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.5836

(12)2-n-Propyl-4-(3-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.5771

(13)3-Isopropyl-4-(4-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²².0 1.5544

(14)3-Isopropyl-4-(3-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²².0 1.5753

(15)5-Isopropyl-2-n-propyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 51° C.

(16)2-n-Propyl-4-(4-cyclohexylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²².0 1.5671

(17)2-n-Propyl-4-(4-cyclohexylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 49.8° C.

(18)3-Methyl-4-(4-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n.sub.D²³.5 1.5623

(19)3-Methyl-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.5 1.5834

(20)2-n-Propyl-4-(3-phenylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.0 1.6059

(21)2-n-Propyl-4-(3-phenylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.6244

(22)3-Ethyl-4-(4-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.0 1.5575

(23) 2-Methyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²².5 1.5961

(24) 2-Allyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²¹.5 1.5884

(25)2-Isopropyl-4-(4-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²¹.5 1.5567

(26)2-Isopropyl-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²¹.5 1.5774

(27)2-Isopropyl-4-(3-methoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n.sub.D²¹.5 1.5704

(28)2-Isopropyl-4-(3-methoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²¹.5 1.5928

(29)2-Tert-butyl-5-methyl-4-(4-ethoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ¹⁸.5 1.5584

(30)2-Tert-butyl-5-methyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ¹⁸.5 1.5781

(31)3-Isopropyl-4-(4-ethoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.0 1.5625

(32)3-Isopropyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.5825

(33)2-n-Propyl-4-(3-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.0 1.5570

(34)2,6-Dimethyl-4-(4-chlorophenoxy)-1-(3,3-dichloro2-propenyloxy)benzene,n_(D) ²².5 1.5784

(35)2,6-Dimethyl-4-(4-chlorophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²².5 1.5970

(36)2-Isopropyl-4-(4-ethoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²².5 1.5616

(37)2-Isopropyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²².5 1.5787

(38)2-Tert-butyl-4-(4-ethoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n.sub.D²³.0 1.5601

(39)2-Tert-butyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.5809

(40)2-Isopropyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.5681

(41)2-Isopropyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.5900

(42)2-Isopropyl-4-(2-chloro-4-ethoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.5 1.5664

(43)2-Isopropyl-4-(2-chloro-4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.5 1.5874

(44) 2-Ethyl-4-(4-ethoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²².5 1.5741

(45)2-Isopropyl-4-(3-chlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.5 1.5700

(46)2,6-Diisopropyl-4-(3-chlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.5 1.5530

(47)2-Isopropyl-4-(3-chlorophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.5 1.5961

(48) 2-Ethyl-4-(4-chlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵.0 1.5821

(49) 2-Ethyl-4-(4-ethoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²².0 1.5701

(50) 2-Ethyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²².0 1.5912

(51)2-n-Propyl-4-(4-ethoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.5 1.5615

(52)2-n-Propyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.5849

(53)3-Sec-butyl-4-(4-ethoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.5 1.5572

(54)2-Sec-butyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.5784

(55) 3-Methyl-4-(4-methoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.5 1.5788

(56) 3-Methyl-4-(4-methoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.5 1.6018

(57) 3-Methyl-4-(4-ethoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵.0 1.5705

(58) 3-Methyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵.0 1.5930

(59) 2-Bromo-4-(3-chlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p. 42.7° C.

(60)2-Bromo-4-(2-chloro-4-trifluoromethylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.3 1.5546

(61) 2-Bromo-4-(3-bromophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²².5 1.6202

(62)2-Bromo-4-(3,5-dichlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²².5 1.5950

(63) 2-Bromo-4-(4-chlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.0 1.6110

(64)2-Bromo-4-(4-trifluoromethylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵.0 1.5616

(65)2-Bromo-4-(2-chloro-4-trifluoromethylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵.5 1.5892

(66) 2-Bromo-4-(3-bromophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.6496

(67)2-Bromo-4-(3,5-dichlorophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.6398

(68) 2-Bromo-4-(3-chlorophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.0 1.6282

(69)2-Bromo-4-(3-bromo-4-(3,3-dichloro-2-propenyloxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.2 1.6208

(70)2-Chloro-4-(3,4-dichlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n.sub.D²³.0 1.5820

(71)2-Chloro-4-(2,4-dichlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n.sub.D²².0 1.6060

(72)2-Chloro-4-(2,4-difluorophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²².0 1.5642

(73) 2-Chloro-4-(4-fluorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²².0 1.5802

(74) 2-Chloro-4-(3-chlorophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.2 1.6248

(75) 2-Chloro-4-(3-fluorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.0 1.5728

(76)2,5-Dichloro-4-(4-(3,3-dichloro-2-propenyloxy)phenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.4 1.5998

(77)2,5-Dichloro-4-(4-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.5 1.5828

(78)2,5-Dichloro-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.5 1.6021

(79)2,6-Dichloro-4-(3-chlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n.sub.D²⁴.2 1.6003

(80)2,6-Dichloro-4-(3,4-dichlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5992

(81)2,6-Dichloro-4-(3,5-difluorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.9 1.5689

(82)2,6-Dichloro-4-(4-chlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n.sub.D²⁴.0 1.5962

(83)2,6-Dichloro-4-(3-fluorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n.sub.D²⁴.0 1.5800

(84)2,6-Dichloro-4-(2-chloro-4-trifluoromethylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.3 1.5546

(85)2,6-Dichloro-4-(3,4-dichlorophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.0 1.6275

(86)2,5-Dichloro-4-(4-chlorophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.0 1.6154

(87)2,5-Dichloro-4-(2,6-dichloro-4-trifluoromethylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 86.1° C.

(88)2,5-Dichloro-4-(2,6-dichloro-4-trifluoromethylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 86.9° C.

(89)2-Chloro-4-(2-chloro-4-trifluoromethylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.6 1.5581

(90)2-Bromo-4-(3-bromo-4-(3,3-dibromo-2-propenyloxy)phenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 80.6° C.

(91) 2-Chloro-4-(4-chlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.0 1.5970

(92) 2-Chloro-4-(3-bromophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²¹.5 1.6112

(93)2-Chloro-4-(3,5-dichlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n.sub.D²¹.5 1.6045

(94)2-Chloro-4-(3,5-dichlorophenoxy)-1-(3,3-dibromo-2-propenyloxy)-benzene,n.sub.D²⁵.5 1.6198

(95) 2-Chloro-4-(3-bromophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵.5 1.6365

(96)2-Chloro-4-(2-chloro-4-trifluoromethylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.5810

(97) 2-Chloro-4-(4-chlorophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.0 1.6232

(98)2-Chloro-4-(3,5-difluorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n.sub.D²⁴.2 1.5691

(99) 2-Chloro-4-(3-chlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 48.8° C.

(100)2-Chloro-4-(3-methylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.8 1.5830

(101)2-Chloro-4-(4-methylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.8 1.5835

(102)2-Bromo-6-chloro-4-(3-chlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.0 1.6139

(103)2-Bromo-6-chloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 59.5° C.

(104)2-Bromo-6-chloro-4-(3,4-dichlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²².0 1.6198

(105)2-Bromo-6-chloro-4-(3,4-dichlorophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.0 1.6395

(106)2-Chloro-5-methyl-4-(4-(2,2,2-trifluoroethoxy)phenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 55.4° C.

(107)2-Chloro-5-methyl-4-(4-(2,2,2-trifluoroethoxy)phenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5645

(108)2-Chloro-5-methyl-4-(4-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.5 1.5723

(109)2-Chloro-5-methyl-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.5 1.5929

(110)2-Bromo-4-(4-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n.sub.D²³.5 1.5836

(111)2-Bromo-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.5 1.6043

(112)2-Trifluoromethyl-4-(4-methoxyphenylthio)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.5 1.5719

(113)2,5-Dichloro-4-(2,4-bistrifluoromethylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 78.5° C.

(114)2,5-Dichloro-4-(2,4-bistrifluoromethylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 74.3° C.

(115)2-Difluoromethyl-4-(3-chlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.5 1.5632

(116)2-Methoxyiminomethyl-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.5 1.5966

(117)2-Methoxymethyl-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵.0 1.5793

(118)2-(2,2-Dibromoethynyl)-4-(4-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵.0 1.6102

(119)2-(2,2-Dibromoethynyl)-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.0 1.6290

(120)2-Ethynyl-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.5 1.6037

(121)2-Difluoromethyl-4-(4-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²².5 1.5461

(122)2-Difluoromethyl-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²².5 1.5677

(123)2-Dibromo-6-nitro-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.6086

(124)2-Trifluoromethyl-4-(4-methoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵.4 1.5572

(125)2-Trifluoromethyl-4-(3-trifluoromethylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.0 1.5282

(126)2-Trifluoromethyl-4-((4-methylthio)phenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5722

(127)2-Trifluoromethyl-4-((4-methylthio)phenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5944

(128)2-Trifluoromethyl-4-(3-methoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.6 1.5418

(129)2-Trifluoromethyl-4-(3-methoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.6 1.5640

(130)2-Trifluoromethyl-4-(3-ethoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.6 1.5369

(131)2-Trifluoromethyl-4-(3-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.6 1.5550

(132)2-Trifluoromethyl-4-(3,5-dimethoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 46.0° C.

(133)2-Trifluoromethyl-4-(3,5-dimethylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5670

(134)2-Trifluoromethyl-4-(3,4-dimethoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5670

(135)2-Trifluoromethyl-4-(3,4-dimethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 76.1° C.

(136)2-Trifluoromethyl-4-(2-chloro-4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5260

(137)2-Trifluoromethyl-4-(4-n-propoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5399

(138)2-Trifluoromethyl-4-(4-n-propoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5552

(139)2-Trifluoromethyl-4-(4-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5322

(140)2-Trifluoromethyl-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5429

(141)2-Trifluoromethyl-4-(4-n-butoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5302

(142)2-Trifluoromethyl-4-(4-n-butoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5510

(143)2-Trifluoromethyl-4-(4-(2,2,2-trifluoroethoxy)phenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5095

(144)2-Trifluoromethyl-4-(4-(2,2,2-trifluoroethoxy)phenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5300

(145)2-Trifluoromethyl-4-(4-phenoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 49.3° C.

(146)2-Trifluoromethyl-4-(4-phenoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 61.9° C.

(147)2-Trifluoromethyl-4-(4-phenylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 59°-63° C.

(148)2-Trifluoromethyl-4-(4-phenylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 61°-62° C.

(149)2-Trifluoromethyl-4-(3-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²¹.6 1.5302

(150)2-Trifluoromethyl-4-(3-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²¹.6 1.5511

(151)2-Trifluoromethyl-4-(4-cyclohexylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ¹⁸.6 1.5416

(152)2-Trifluoromethyl-4-(4-cyclohexylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 71.5° C.

(153)4-(4-Isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)-5,6,7,8-tetrahydronaphthalene,n_(D) ¹⁸.6 1.5575

(154)4-(4-Isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)-5,6,7,8-tetrahydronaphthalene,n_(D) ¹⁸.6 1.5812

(155)2-Trifluoromethyl-4-(2,6-dichloro-4-trifluoromethylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ¹⁸.6 1.5220

(156)2-Trifluoromethyl-4-(2.6-dichloro-4-trifluoromethylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ¹⁸.6 1.5402

(157)2-Trifluoromethyl-4-(4-cyclopentylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²².5 1.5472

(158)2-Trifluoromethyl-4-(4-cyclopentylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁰.8 1.5620

(159)2-Trifluoromethyl-4-(4-(2-n-pentyl)phenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5278

(160)2-Trifluoromethyl-4-(4-(2-n-pentyl)phenoxy)-1-(3.3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5468

(161)2-Trifluoromethyl-4-(4-tert-pentylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5308

(162)2-Trifluoromethyl-4-(4-tert-pentylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5506

(163)2-Trifluoromethyl-4-(3-phenylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.9 1.5827

(164)2-Trifluoromethyl-4-(3-phenylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.9 1.5999

(165)2-Trifluoromethyl-(3-phenoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.9 1.5548

(166)2-Trifluoromethyl-(3-phenoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.9 1.5801

(167)2-Trifluoromethyl-4-(5,6,7,g-tetrahydro-2-naphthoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.9 1.5432

(168)2-Trifluoromethyl-4-(5,6,7,g-tetrahydro-2-naphthoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.9 1.5678

(169)2-Trifluoromethyl-4-(5-indanoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.4 1.5504

(170)2-Trifluoromethyl-4-(5-indanoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n.sub.D²³.4 1.5692

(171)2-Trifluoromethyl-4-(3,5-bis(trifluoromethyl)phenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.4 1.4832

(172)2-Trifluoromethyl-4-(3,5-bis(trifluoromethyl)phenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.5018

(173)2-Trifluoromethyl-4-(4-sec-butylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵.0 1.5282

(174)2-Trifluoromethyl-4-(4-sec-butylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵.0 1.5479

(175)2-Trifluoromethyl-4-(4-tert-octylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵.0 1.5201

(176)2-Trifluoromethyl-4-(4-tert-octylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵.0 1.5397

(177)2-Trifluoromethyl-4-(4-tert-butylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵.0 1.5283

(178)2-Trifluoromethyl-4-(4-tert-butylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵.0 1.5481

(179)2-Trifluoromethyl-4-(3-(3,3-dichloro-2-propenyloxy)phenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5571

(180)2-Trifluoromethyl-4-(3-(3,3-dibromo-2-propenyloxy)phenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5878

(181)2-Trifluoromethyl-4-(13-naphthoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵.5 1.5859

(182)2-Trifluoromethyl-4-(13-naphthoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵.6 1.5953

(183)2-Trifluoromethyl-4-(3-tert-butylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵.5 1.5304

(184)2-Trifluoromethyl-4-(3-tert-butylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵.6 1.5465

(185)2-Trifluoromethyl-4-(4-(1-hydroxy-n-propyl)phenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.0 1.5401

(186)2-Trifluoromethyl-4-(2,4-diisopropylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.4 1.5252

(187)2-Trifluoromethyl-4-(2,4-diisopropylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.4 1.5433

(188)2-Trifluoromethyl-4-(5,6,7,8-tetrahydro-1-naphthoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.4 1.5538

(189)2-Trifluoromethyl-4-(5,6,7,8-tetrahydro-1-naphthoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.4 1.5688

(190)2-Trifluoromethyl-4-(3-chlorophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.0 1.5419

(191)2-Trifluoromethyl-4-(3-chlorophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²².3 1.5700

(192)2-Trifluoromethyl-4-(3-(trifluoromethyl)phenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵.5 1.5081

(193)2-Trifluoromethyl-4-(4-ethoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵.5 1.5375

(194)2-Trifluoromethyl-4-(4-trifluoromethyl)phenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵.0 1.5091

(195)2-Trifluoromethyl-4-(4-trifluoromethoxy)phenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵.0 1.4948

(196)2-Trifluoromethyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.0 1.5480

(197)2-Trifluoromethyl-4-(4-methoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.0 1.5448

(198)2-Trifluoromethyl-4-(3,4-methylenedioxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5480

(199)2-Trifluoromethyl-4-(4-(trifluoromethyl)phenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵.0 1.5282

(200)2-Trifluoromethyl-4-(4-(trifluoromethoxy)phenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,

(201)2,5-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,resinous

(202)2,5-Dichloro-4-(3-trifluoromethyl-5-chloro-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 60.9° C.

(203)2,5-Dichloro-4-(3-trifluoromethyl-5-chloro-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 49.8° C.

(204)2,5-Dichloro-4-(3,6-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 48.6° C.

(205)2,5-Dichloro-4-(3,6-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 73.9° C.

(206)2,5-Dichloro-4-(3-bromo-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 95.4° C.

(207)2,5-Dichloro-4-(3-bromo-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 101.4° C.

(208)3,5-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 97.8° C.

(209)3,5-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 84.4° C.

(210)3,5-Dichloro-4-(3-bromo-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 90.70° C. (211)3,5-Dichloro-4-(3-bromo-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 85.0° C.

(212)3,5-Dichloro-4-(3,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 77.6° C.

(213)3,5-Dichloro-4-(3,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 79.5° C.

(214)3-Chloro-4-(3,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.0 1.5130

(215)3-Methyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 48.7° C.

(216)3-Chloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 46.2° C.

(217)2-Methyl-4-(3,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²¹.5 1.5081

(218)2-Methyl-4-(3,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²¹.5 1.5299

(219)3-Methyl-4-(3,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5019

(220)3-Methyl-4-(3,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5271

(221)3-Chloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 42.8° C.

(222)3-Methyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 65.3° C.

(223)2,5-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 87.2° C.

(224)2-Chloro-4-(4,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.0 1.5370

(225)3-Chloro-4-(4,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.0 1.5359

(226)2-Chloro-4-(3,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 54.5° C.

(227)3-Chloro-4-(3,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.2 1.5161

(228)2,5-Dichloro-4-(3,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 75°-76° C.

(229)2,5-Dichloro-4-(3,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 73°-74° C.

(230)2,6-Dichloro-4-(3,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 66.7° C.

(231)2,6-Dichloro-4-(3,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 76.2° C.

(232)2-Chloro-4-(4,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.0 1.5242

(233)3-Chloro-4-(4,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.0 1.5196

(234)2-Chloro-4-(3,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 58.8° C.

(235)2-Chloro-4-(6-chloro-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 68.220 C.

(236)2,6-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²².0 1.5572

(237)2-Bromo-6-chloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-chloro-2-propenyloxy)benzene,m.p., 59.5° C.

(238)2,6-Dibromo-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 71.2° C.

(239)2,6-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 58.2° C.

(240)2-Trifluoromethyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.0 1.5182

(241)2-Trifluoromethyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵.0 1.5310

(242)2-Bromo-4-(3-Chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.0 1.5780

(243)2,6-Dimethyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.0 1.5413

(244)2,6-Dimethyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.0 1.5633

(245)2,5-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 105.9° C.

(246)2,5-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 104.2° C.

(247)2-Tert-butyl-5-methyl-4-(5-tert-butyl-2-methyl-4-(3,3-dichloro-2-propenyloxy)phenylthio)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵ 1.5643

(248)2-Bromo-4-(1-methyl-1-(4-isopropoxyphenyl))ethyl-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 55.7° C.

(249)2-Bromo-4-(1-methyl-1-(4-(3,3-dichloro-2-propenyloxy)phenyl))ethyl-2-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵ 1.5997

(250)2-Chloro-4-(1-methyl-1-(4-isopropoxyphenyl))ethyl-1-(3,3-dichloro-1-propenyloxy)benzene,n_(D) ²⁵ 1.5683

(251)2-Chloro-4-(1-methyl-1-(4-isopropoxyphenyl))ethyl-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵ 1.5821

(252)2-Chloro-4-(1-methyl-1-(4-bromophenyl))ethyl-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴ 1.6007

(253)2-Chloro-4-(1-methyl-1-(4-bromophenyl))ethyl-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴ 1.6172

(254)2,6-Dichloro-4-(1-methyl-1-(4-bromophenyl))ethyl-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵ 1.5752

(255)2,6-Dichloro-4-(1-methyl-1-(4-bromophenyl))ethyl-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵ 1.6165

(256)2-n-Propyl-4-(4-ethoxyphenylthio)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁰ 1.6152

(257)2-n-Propyl-4-(4-isopropoxypbenylthio)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁰.5 1.5851

(258)2-n-Propyl-4-(4-isopropoxyphenylthio)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁰.5 1.6041

(259)2-Ethyl-4-(4-isopropoxyphenylthio)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.0 1.5911

(260)2-Ethyl-4-(4-isopropoxyphenylthio)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.6105

(261)2-Bromo-4-(4-isopropoxyphenylthio)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁰.5 1.6202

(262)2-Bromo-4-(4-isopropoxyphenylthio)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²¹.0 1.6413

(263)2-Ethyl-4-(1-methyl-1-(4-isopropoxyphenyl))ethyl-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ¹⁹ 1.5794

(264)2-n-Propyl-4-(1-methyl-1-(4-isopropoxyphenyl))ethyl-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³ 1.5716

(265)2-Bromo-4-(4-ethoxyphenylthio)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³ 1.6286

(266)2-Bromo-4-(4-ethoxyphenylthio)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³ 1.6509

(267)2-Bromo-4-(4-(3,3-dichloro-2-propenyloxy)phenylthio)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵ 1.6360

(268)2-n-Butyl-4-(4-ethoxyphenylthio)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²¹ 1.6071

(269)2-Bromo-4-(1-trifluoromethyl-1-(4-ethoxyphenyl)-2,2,2-trifluoroethyl)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴ 1.5476

(270)2,6-Dibromo-4-(1-trifluoromethyl-1-(4-ethoxyphenyl)-2,2,2-trifluoroethyl)-1-(3,3-dibromo-2-propenyloxy)benzene,resinous

(271)2-Trifluoromethyl-4-(4-methoxyphenylthio)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.5 1.5523

(272)2-n-Propyl-4-(4-ethoxyphenylthio)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁰ 1.5942

(273)2-Bromo-4-(4-chlorophenylthio)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵ 1.65 14

(274)2-Bromo-4-(4-chlorophenylthio)-1-(3,3-dibromo-2-propenyloxy)benzene,N_(D) ²³ 1.6757

(275)2-Bromo-4-(1-methyl-1-(4-ethoxyphenyl))ethyl-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁵ 1.5869

(276)2-Bromo-4-(1-methyl-1-(4-ethoxyphenyl))ethyl-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁵ 1.6018

(277)2-Bromo-4-(1-methyl-1-(4-isopropoxyphenyl))ethyl-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.5 1.5793

(278)2-Bromo-4-(1-methyl-1-(4-isopropoxyphenyl))ethynyl-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.0 1.5778

(279)2-Bromo-4-(1-methyl-1-(4-isopropoxyphenyl))ethyl-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.3 1.5821

(280)2-Bromo-4-(1-(4-isopropoxyphenyl))ethyl-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.3 1.6018

(281)2-Chloro-6-(3-chlorophenoxy)-3-(3,3-dichloro-2-propenyloxy)benzene,

(282)2-n-Propyl-4-(4-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²².5 1.556

(283)2-Bromo-4-(4-isopropoxyphenyl)methyl-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.5 1.5681

(284)2-Bromo-4-(4-isopropoxyphenyl)methyl-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.5 1.6002

(285)2,6-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyl)amino)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 77.8° C.

(286)2,6-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyl)amino-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 106.1 ° C.

(287)2,6-Dibromo-4-(4-isopropyloxyphenyl)sulfonyl-1-(3,3-dichloro-2-propenyloxy)benzene,¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.35 (6H, d, J=6.0 Hz), 4.62 (1H, septet,J=6.0 Hz), 4.68 (2H, d, J=6.7 Hz), 6.31 (1H, t, J=6.7 Hz), 6.96 (2H, d,J=7.1 Hz), 7.83 (2H, d, J=7.0 Hz), 8.04 (2H, s), resinous

(288)2,6-Dibromo-4-(4-isopropyloxyphenyl)sulfonyl-1-(3,3-dibromo-2-propenyloxy)benzene,¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.34 (6H, d, J=6.0 Hz), 4.57 (2H, d, J=6.7Hz), 4.60 (1H, septet, J=6.0 Hz), 6.85 (1H, t, J=6.6 Hz), 6.95 (2H, d,J=8.0 Hz), 7.81 (2H, d, J=7.9 Hz), 8.04 (2H, s), resinous

(289)3,5-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenylamino)benzene,glassy

(290)3,5-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenylamino)benzene,glassy

(291)2-Ethoxy-4-(4-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.5 1.5580

(292)2-Ethoxy-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 69.1° C.

(293)2-Bromo-4-(1-ethyl-1-(4-isopropoxyphenoxy)propyl)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.5 1.5685

(294)2-Bromo-4-(1-methyl-1-(4-isopropoxyphenoxy)propyl)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.5 1.5851

(295)3-Methyl-4-(4-ethoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.0 1.5705

(296) 3-Methyl-4-(4-ethoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.0 1.5942

(297)3,5-Dimethyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁶.0 1.5410

(298)3,5-Dimethyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 60.2° C.

(299)3-Bromo-4-(3-bromo-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.6 1.5624

(300)3-Bromo-4-(3-bromo-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.6 1.5853

(301)3-Bromo-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.6 1.5581

(302)3-Bromo-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁴.6 1.5748

(303)2,3-Dimethyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 54.9

(304)2-(Allyloxyimino)-4-(4-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³ 1.5726

(305)2-(Allyloxyimino)-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³ 1.5972

(306)2-Isopropyl-4-(4-isopropoxyphenoxy)phenoxy-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³ 1.5748

(307)2-Isopropyl-4-(4-isopropoxyphenoxy)phenoxy-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³ 1.5860

(308)3-Methyl-4-(2-methyl-3,4-ethylenedioxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²².5 1.5877

(309)2,3-Dimethyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³ 1.5444

(310)2,3,6-Trimethyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 49.9° C.

(311)2,3,6-Trimethyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 151.3° C.

(312) 2-Isopropyl-4-(2-methyl-3,4-ethylenedioxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²² 1.5718

(313)2-Isopropyl-4-(2-methyl-3,4-ethylenedioxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²² 1.5908

(314)2,6-Dichloro-4-(1-methyl-1-(3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl)ethyl)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²¹.5 1.5726

(315)2,6-Dichloro-4-(l-methyl-1-(3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl)ethyl)-1-(3,3-dibromo-2-propenyloxy)benzene,glassy

(316)3-Tert-butyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²² 1.5388

(317)3-Tert-butyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²² 1.5591

(318)2,6-Dimethyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²² 1.5400

(319)2,6-Dimethyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²² 1.5621

(320)2-Isopropyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²² 1.5398

(321)2-Isopropyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²² 1.5587

(322)2,6-Dimethyl-4-(5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²² 1.5342

(323)2,6-Dimethyl-4-(5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²² 1.5549

(324)3,5-Dichloro-4-(5-nitro-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²¹ 1.6028

(325)3,5-Dichloro-4-(5-nitro-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²¹ 1.6247

(326)2,6-Dichloro-4-(2,4-dinitrophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 74.9° C.

(327)2-Bromo-4-(1-methyl-1-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl)ethyl)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³ 1.5725

(328)2-Bromo-4-(1-methyl-1-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl)ethyl)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³ 1.5942

(329)2-Bromo-4-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³ 1.5791

(330)2-Bromo-4-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³ 1.5849

(331)2-Methyl-5-chloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) 18.5 1.5530

(332)2-Methyl-5-chloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ⁸.5 1.5687

(333)2-(1-Methyl-2-propenyl)-4-(4-isopropoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²².5 1.5611

(334)2-(1-Methyl-2-propenyl)-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²².5 1.5791

(335)3-Chloro-5-bromo-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 95.5° C.

(336)3-Chloro-5-bromo-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 94.3° C.

(337)3,5-Dichloro-4-(4-cyanophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 119.2° C.

(338)2,6-Dibromo-4-(3-chloro-5-trifluoromethyl-2-pyridylamino)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 117.1° C.

(339)3,5-Dichloro-4-(3-bromo-5-nitro-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 91.6° C.

(340)3-Methyl-4-(3-methoxyphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³ 1.5787

(341)2-Isopropyl-5-chloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.3 1.5380

(342)2-Isopropyl-5-chloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.3 1.5552

(343)2-Bromo-4-(2-methyl-1-(4-ethoxyphenyl))propyl-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.5 1.5791

(344)2-Bromo-4-(2-methyl-1-(4-ethoxyphenyl))propyl-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 64.3° C.

(345)2-Bromo-4-(2-methyl-1-(4-isopropoxyphenyl))propyl-1-(3,3-dichloro2-propenyloxy)benzene,n_(D) ²³.5 1.5694

(346)2-Bromo-4-(2-methyl-1-(4-ethoxyphenyl))propyl-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.5 1.5820

(347)2-Isopropyl-4-(2-methyl-4-(3,3-dichloro-2-propenyloxy))phenoxy-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁰ 1.573

(348)2-Isopropyl-4-(2-methyl-4-(3,3-dichloro-2-propenyloxy))phenoxy-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²⁰ 1.6070

(349)3,5-Dichloro-4-(2,6-dichloro-4-trifluoromethyl)phenoxy-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴ 1.5735

(350)3,5-Dichloro-4-(2-fluoro-4-nitrophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 94.2° C.

(351)3,5-Dichloro-4-(2-fluoro-4-nitrophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,m.p., 79.3° C.

(352)3,5-Dichloro-4-(2-chloro-4-nitrophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²³.5 1.6172

(353)3,5-Dichloro-4-(2-chloro-4-nitrophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³.5 1.6396

(354)3,5-Dichloro-4-(6-chloro-3,5-bistrifluoromethyl-2-pyridyloxy)-1-(3,3-dichloro-2-propenyloxy)benzene,m.p., 108.9° C.

(355)3,5-Dichloro-4-(2-nitro-4-trifluoromethylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²¹.5 1.5706

(356)3,5-Dichloro-4-(2-nitro-4-trifluoromethylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²¹.5 1.5870

(357)3,5-Dichloro-4-(2,4-dinitro-6-trifluoromethylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²¹.5 1.5778

(358)3,5-Dichloro-4-(2,4-dinitro-6-trifluoromethylphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²¹.5 1.588

(359)3,5-Dichloro-4-(2-trifluoromethyl-4-nitrophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²¹.5 1.5757

(360)3,5-Dichloro-4-(2-trifluoromethyl-4-nitrophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²¹.5 1.5962

(361)3,5-Dichloro-4-(2,4-bistrifluoromethylphenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴ 1.5333

(362)3,5-Dichloro-4-(2,4-dinitrophenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene,n_(D) ²³ 1.6290

(363)3-Methyl-4-(4-(2,2,2-trifluoroethoxy)phenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.5 1.5382

(364) 3-Methyl-4-(4-nitrophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²⁴.5 1.6057

(365)3,5-Dichloro-4-(4-acetamidophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,glassy

(366)3,5-Dichloro-4-(4-trifluoromethylacetamidophenoxy)-1-(3,3-dichloro-2-propenyloxy)benzene,n_(D) ²².5 1.5708

(367)3,5-Dichloro-4-(2,6-dichloro-4-trifluoromethylphenoxy)-1-(3,3-dibromo-2-allyloxy)benzene,n_(D) ²⁴.5 1.5878

The following will describe some production examples of the intermediatecompound of the formula II.

EXAMPLE 11

Production of intermediate compound 67

First, 1.07 g of hydroquinone monobenzyl ether and 500 ml of carbontetrachloride were charged into a reaction vessel, and a solutionprepared by dissolving 1.01 g of t-butyl hypochlorite in_(D) ¹⁰ ml ofcarbon tetrachloride was slowly added dropwise with stirring under icecooling. After 24 hours, the reaction solution was poured into water andthe organic layer (carbon tetrachloride) was separated. Then, theorganic layer was washed with water, dried over anhydrous magnesiumsulfate and concentrated to give a crude product. This crude product wassubjected to silica gel chromatography to give 0.85 g of2,6-dichloro-4-benzyloxyphenol (yield, 59%).

Then, 0.85 g of 2,6-dichloro-4-benzyloxyphenol, 0.48 g of potassiumcarbonate, 0.75 g of 2,3-dichloro-5-trifluoromethylpyridine and 10 ml ofN,N-dimethylformamide were charged into a reaction vessel, and stirredat 85° to 90° C. for 3 hours. Then, the reaction solution was cooled toroom temperature, poured into water and extracted twice with 50 ml ofdiethyl ether. The ether layers were combined, washed with water, driedover anhydrous magnesium sulfate and then concentrated to give a crudeproduct. This crude product was subjected to silica gel chromatographyto give 1.39 g of3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-benzyloxybenzene,(yield, 98%).

Then, 1.39 g of3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-1-benzyloxybenzene,and 20 ml of methylene chloride were charged into a reaction vessel, anda solution of boron tribromide (1.63 g) in methylene chloride (10 ml)was added dropwise with stirring under ice cooling (-10° C. to 0° C.).After stirring for one hour under ice cooling, the mixture was pouredinto 10% hydrochloric acid and extracted twice with 50 ml of methylenechloride. Then, the organic layers were combined, washed with water,dried over anhydrous magnesium sulfate and concentrated to give a crudeproduct. This crude product was subjected to silica gel columnchromatography to give 1.03 g of3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenol (yield,93%), m.p., 152.6° C.

EXAMPLE 12

Production of intermediate compound 63

To a solution prepared by dissolving 2.8 g of hydroquinone in 20 ml ofN,N-dimethylformamide, 1.39 g of sodium hydride (60% oil-based) wasadded, slowly, with stirring under ice cooling. After completion of thegeneration of hydrogen gas from the reaction solution, a solutionprepared by dissolving 5 g of 2,3-dichloro-5-trifluoromethylpyridine in10 ml of N,N-dimethylformamide was added dropwise. After stirring atroom temperature for 3 hours, the reaction solution was poured intoice-water, and extracted twice with 200 ml of diethyl ether. Then, theether layers were combined, washed with water, dried over anhydrousmagnesium sulfate and then concentrated to give a crude product. Thiscrude product was subjected to silica gel chromatography to give 2.88 gof 4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenol (yield, 43%).

To a solution prepared by dissolving the resulting 2.88 g of4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenol in 300 ml ofchloroform, 4.80 g of tetra-n-butylammonium tribromide was slowly addedwith stirring under room temperature. After 12 hours, the reactionsolution was concentrated, and the residue was extracted twice with 100ml of diethyl ether. Then, the ether layers were combined, washed withwater, dried over anhydrous magnesium sulfate and then concentrated togive a crude product. This crude product was subjected to silica gelchromatography to give 2.53 g of2-bromo-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenol (yield, 69%).

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.54 (1H, br), 7.06 (3H, brs), 7.33 (1H,d), 7.97 (1H, d), 8.27 (1H, d)

EXAMPLE 13

Production of intermediate compound 5

First, 20.4 g of 2-isopropylphenol and 750 ml of chloroform were chargedinto a reaction vessel, and 80 g of tetra-n-butylammonium tribromide wasadded at room temperature (about 20° C. ) with stirring and the mixturewas stirred at room temperature for additional 24 hours. To the reactionsolution, 750 ml of a saturated sodium sulfite solution was added, andthe mixture was shaken vigorously to concentrate the chloroform layer.To the residue, 500 ml of diethyl ether and 500 ml of 10% hydrochloricacid were added, and the mixture was shaken vigorously. The ether layerwas dried over anhydrous magnesium sulfate and concentrated to give 32 gof 4-bromo-2-isopropylphenol (yield, 100%).

A mixture of 32 g of 4-bromo-2-isopropylphenol, 25.7 g of benzylbromide, 23 g of potassium carbonate and 300 ml of N,N-dimethylformamidewas stirred at room temperature for 24 hours. The reaction solution waspoured into ice-water, acidified by adding 10% hydrochloric acid andthen extracted with 500 ml of diethyl ether. Then, the ether layer waswashed with a saturated saline solution, dried over anhydrous magnesiumsulfate and concentrated. The residue was subjected to silica gel columnchromatography to give 30 g of 4-bromo-2-isopropylphenyl benzyl ether(yield, 65%).

A mixture of 10 g of 4-bromo-2-isopropylphenyl benzyl ether, 4.7 g of4-ethoxyphenol, 4.7 g of potassium carbonate, 0.30 g of copper powder,0.30 g of cuprous iodide and 30 ml of pyridine was stirred at 130° C. to140° C. for 24 hours. The reaction solution was cooled to roomtemperature, poured into ice-water and then acidified by adding 10%hydrochloric acid. The solution was extracted with 100 ml of diethylether, washed in turn with 10% hydrochloric acid, an aqueous 10% sodiumhydroxide solution and a saturated saline solution, dried over anhydrousmagnesium sulfate and then concentrated. The residue was subjected tosilica gel column chromatography to give 4.4 g of4-(4-ethoxyphenoxy)-2-isopropylphenyI benzyl ether (yield, 37%).

Then, 4.4 g of 4-(4-ethoxyphenoxy)-2-isopropylphenyl benzyl ether and100 ml of ethyl acetate were charged into a reaction vessel, and air inthe vessel was replaced with nitrogen. Then, 0.50 g of 5%palladium-carbon was added, and nitrogen in the vessel was replaced withhydrogen, followed by vigorous stirring at room temperature for 24hours. After hydrogen in the vessel was replaced with nitrogen, thereaction vessel was filtered with Celite, and the filtrate wasconcentrated. The residue was subjected to silica gel chromatography togive 3.1 g of 2-isopropyl-4-(4-ethoxyphenoxy)phenol (yield, 93%).

n_(D) ²⁵.5 1.5612

¹ H-NMR (CDCl₃ /TMS) 67 (ppm): 1.22 (6H, d), 1.41 (3H, t), 3.13-3.22(1H, m), 4.01 (2H, q), 4.69 (1H, s), 6.62-6.93 (7H, m)

EXAMPLE 14

Production of intermediate compound 87

First, 7.44 g of 4,4'-bispropylidenebiphenol, 4.63 g of 2-bromopropane,4.53 g of Potassium carbonate and 50 ml of N,N dimethylformide werecharged into a reaction vessel, and the mixture was stirred at an oilbath temperature of 80° C. to 90° C. for 6 hours. The reaction solutionwas poured into water and extracted three times with 30 ml of ethylacetate. Then, the ethyl acetate layers were combined, washed withwater, dried over anhydrous magnesium sulfate and concentrated to give acrude product. This crude product was subjected to silica gelchromatography to give 3.89 g of4-(1-(4-isopropyloxyphenyl)-1-methylethyl)phenol (yield, 44%).

To a solution of 4-(1-(4-isopropyloxyphenyl)-1-methylethyl)phenol (0.51g) in carbon tetrachloriode (1.3 ml), a solution prepared by dissolving0.23 g of tert-butyl hypochlorite in 0.5 ml of carbon tetrachloride wasadded dropwise with stirring under ice cooling. After 30 minutes, an icebath was removed, and the mixture was stirred at room temperature for 30minutes. The reaction solution was poured into water and extracted threetimes with 5 ml of carbon tetrachloride. Then, the carbon tetrachloridelayers were combined, washed with water, dried over anhydrous magnesiumsulfate and then concentrated to give a crude product. This crudeproduct was subjected to silica gel column chromatography to give 0.49 gof 4-(1-(4-isopropyloxyphenyl)-1-methylethyl)-2-chlorophenol (yield,85%).

n_(D) ²⁶ 1.5557;

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.33 (6H, d), 1.62 (6H, s), 5.43 (1H, s),6.78 (2H, d), 6.89 (1H, d), 7.02 (1H, dd), 7.11 (2H, d), 7.18 (1H, d)

EXAMPLE 15

Production of intermediate compound 23

A mixture of 6.3 g of 4-isopropoxyphenol, 10.5 g of 4-bromophenyl benzylether, 8.3 g of potassium carbonate, 0.5 g of copper powder, 0.5 g ofcuprous chloride and 3.5 g of pyridine was stirred at 130° C. to 140° C.for 24 hours. The reaction solution was cooled to room temperature,pound into water and then acidified by adding 10% hydrochloric acid. Thesolution was extracted with 100 ml of diethyl ether, washed in turn with10% hydrochloric acid, an aqueous 10% sodium hydroxide solution and asaturated saline solution, dried over anhydrous magnesium sulfate andthen concentrated. The crude product was subjected to silica gel columnchromatography to give 4.3 g of 4-(4-isopropyloxy)phenyl benzyl ether(yield, 32%).

Then, 4.3 g of 4-(4-isopropyloxy)phenyl benzyl ether and 100 ml of ethylacetate were charged into a reaction vessel, and air in the vessel wasreplaced with nitrogen. Then, 0.50 g of 10% palladium-carbon was added,and nitrogen in the vessel was replaced with hydrogen, followed byvigorous stirring at room temperature for 24 hours. After hydrogen inthe vessel was replaced with nitrogen, the reaction vessel was filteredwith Celite, and the filtrate was concentrated. The residue wassubjected to silica gel column chromatography to give 2.8 g of4-(4-isopropoxyphenoxy)phenol (yield, 89%).

To a mixture of 1.23 g of 4-(4-isopropoxyphenoxy)phenol, 1.4 g ofpotassium carbonate and 10 ml of N,N-dimethylformamide 0.65 ml of allylbromide was added dropwise at room temperature with stirring. After 24minutes, the reaction solution was poured into water, and acidified byadding 10% hydrochloric acid. The solution was extracted with 50 ml ofdiethyl ether, washed in turn with 10% hydrochloric acid, an aqueous 10%sodium hydroxide and a saturated saline solution, dried over anhydrousmagnesium sulfate and then concentrated. The residue was subjected tosilica gel column chromatography to give 0.98 g of4-(4-isopropoxyphenoxy)phenyl allyl ether (yield, 69%).

Then, 0.98 g of 4-(4-isopropoxyphenoxy)phenyl allyl ether was heated at190° C. to 200° C. for 6 hours with stirring. The reaction product wascooled to room temperature and then subjected to silica gel columnchromatography to give 0.85 g of 2-allyl-4-(4-isopropoxyphenoxy)phenol(yield, 87%).

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.32 (6H, d), 3.35-3.38 (2H, m), 4.41-4.51(1H, m), 4.77 (1H, s), 5.11-5.20 (2H, m), 5.97-6.07 (1H, m), 6.73-6.91(7H, m)

EXAMPLE 16

Production of intermediate compound 29

First, 41.33 g of 2-trifluoromethylphenol and 1800 ml of chloroform werecharged into a reaction vessel, and 129.16 g of tetra-n-butylammoniumtribromide was slowly added at room temperature over about one hour withstirring. After stirring at room temperature for 72 hours, the reactionsolution was concentrated. Then, 500 ml of 10% hydrochloric acid wasadded to the resultant residue, and the mixture was extracted four timeswith 200 ml of diethyl ether. The ether layers were combined, washedwith water, dried over anhydrous magnesium sulfate and then concentratedto give 49.5 g of 4-bromo-2-trifluoromethylphenol as a crude product(yield, 81%).

Then, 8.47 g of 4-bromo-2-trifluoromethylphenol, 5.34 g of potassiumcarbonate, 4.49 g of benzyl chloride and 100 ml of N,N-dimethylformamidewere charged into a reaction vessel, and stirred under ice cooling.After 24 hours, the reaction solution was poured into ice-water andextracted three times with 50 ml of diethyl ether. The ether layers werecombined, washed with an aqueous 10 % sodium hydroxide solution, driedover anhydrous magnesium sulfate and then concentrated to give a crudeproduct. This crude product was subjected to silica gel chromatographyto give 9.38 g of 4-bromo-2-trifluoromethyl-1-benzyloxybenzene, (yield,81%).

Then, 5.10 g of 4-bromo-2-trifluoromethyl-1-benzyloxybenzene, 2.34 g ofp-ethoxyphenol, 2.13 g of potassium carbonate, 100 mg of copper and 200mg of cuprous chloride were charged into a reaction vessel, and stirredat 130° C. to 140° C. for 5 hours. The reaction solution was cooled toroom temperature, poured into ice-water and then acidified by adding 10%hydrochloric acid. The solution was extracted twice with 100 ml ofdiethyl ether. Then, the ether layers were combined, washed with water,dried over anhydrous magnesium sulfate and concentrated to give a crudeproduct. This crude product was subjected to silica gel chromatographyto give 2.50 g of2-trifluoromethyl-4-(4-ethoxyphenoxy)-1-benzyloxybenzene, (yield, 41%).

Then, 2.50 g of2-trifluoromethyl-4-(4-ethoxyphenoxy)-1-benzyloxybenzene, 100 ml ofethyl acetate and 0.50 g of 10% palladium-carbon were charged into areaction vessel, and air in the vessel was replaced with nitrogen. Then,nitrogen was replaced with hydrogen at room temperature with stirring.After stirring at room temperature for 24 hours, the reaction solutionwas filtered, and the filtrate was concentrated to give a crude product.This crude product was subjected to silica gel chromatography to give1.75 g of 2-trifluoro-4-(4-ethoxyphenoxy)phenol (yield, 91%).

n_(D) ²³.5 1.5322

Other examples of the intermediate compound of the formula II will bedescribed below.

1) 2-n-Propyl-4-(4-ethoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 0.96 (3H, t), 1.41 (3H, t), 1.55-1.67 (2H,m), 2.53 (2H, t), 4.01 (2H, q), 4.62 (1H, s), 6.70-6.93 (7H, m)

2) 2-Isopropyl-4-(2-chloro-4-ethoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.23 (6H, d), 1.41 (3H, t), 3.12-3.22 (1H,m), 4.01 (2H, q), 4.62 (1H, s), 6.56-6.99 (6H, m)

3) 2-Ethyl-4-(4-ethoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.20 (3H, t), 1.39 (3H, t), 2.58 (2H, q),3.99 (2H, q), 4.54 (1H, s), 6.57-7.08 (7H, m)

4) 2-Sec-butyl-4-(4-ethoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 0.86 (3H, t), 1.19 (3H, d), 1.40 (3H, t),1.46-1.68 (2H, m), 2.87-2.98 (1H, m), 4.00 (2H, q), 4.62 (1H, s),6.62-6.90 (m, 7H)

5) 2-Isopropyl-4-(4-ethoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.22 (6H, d), 1.41 (3H, t), 3.13-3.22 (1H,m), 4.01 (2H, q), 4.69 (1H, s), 6.62-6.93 (7H, m)

6) 2-Tert-butyl-4-(4-ethoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.39 (9H, s), 1.41 (3H, t), 4.00 (2H, q),4.75 (1H, s),6.56-6.98 (7H, m)

7) 2-Isopropyl-4-(4-ethoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.23 (6H, d), 3.13-3.22 (1H, m), 3.77 (3H,s), 4.67 (1H, s), 6.49-7.21 (7H, m)

8) 2-n-Propyl-4-(3-ethoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 0.96 (3H, t), 1.38 (3H, t), 1.58-1.68 (2H,m), 2.55 (2H,t), 3.98 (2H, q), 4.65 (1H, s), 6.46-7.20 (7H, m)

9) 2-Methyl-4-(4-ethoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.40 (3H, t), 2.20 (3H, s), 4.00 (2H, q),4.58 (1H, s), 6.70-6.91 (7H, m)

10) 2-Isopropyl-4-(4-isopropoxyphenoxy)phenol

¹ H-NMR (CDCl₃ TMS) δ (ppm): 1.22 (6H, d), 1.32 (6H, d), 3.14-3.23 (1H,m), 4.41-4.49 (1H, m), 4.61 (1H, s), 6.63-6.90 (7H, m)

11) 2-Allyl-4-(4-ethoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.40 (3H, t), 3.35-3.38 (2H, m), 4.01 (2H,q), 4.78 (1H, s), 5.12-5,19 (2H, m), 5.92-6.05 (1H, m), 6.75-6.92 (7H,m)

12) 2-Chloro-5-methyl-4-(4-2,2,2-trifluoroethoxyphenoxy)phenol

n_(D) ²³.5 1.5342

13) 2-Isopropyl-4-(4-ethoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.18 (6H, d), 1.39 (3H, t), 3.18-3.27 (1H,m), 3.99 (2H, q), 4.65 (1H, s), 6.57-6.81 (7H, m)

14) 2-n-Propyl-4-(4-isopropoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 0.96 (3H, t), 3.32 (6H, d), 1.55-1.68 (2H,m), 2.54 (2H, t), 4.41-4.49 (1H, m), 4.52 (1H, s), 6.70-6.90 (7H, m)

15) 3-Isopropyl-4-(4-isopropoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.18 (6H, d), 1.31 (6H, d), 3.17-3.28 (1H,m), 4.39-4.49 (1H, m), 4.71 (1H, s), 6.57-6.81 (7H, m)

16) 2-n-Propyl-4-(4-cyclohexylphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 0.97 (3H, t), 1.15-1.90 (12H, m),2.41-2.58 (3H, m), 4.62 (1H, s), 6.62-7.23 (7H, m)

17) 3-Isopropyl-4-(4-ethoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.18 (6H, d), 1.40 (3H, t), 3.17-3.28 (1H,m), 3.99 (2H, q), 4.64 (1H, s), 6.57-6.81 (7H, m)

18) 3-Methyl-4-(4-isopropoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.31 (6H, d), 2.18 (3H, s), 4.39-4.48 (1H,m), 4.54 (1H, s), 6.59-6.84 (7H, m)

19) 3-Ethyl-4-(4-isopropoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.17 (3H, t), 1.31 (6H, d), 2.58 (2H, q),4.39-4.49 (1H, m), 4.62 (1H, s), 6.58-6.80 (7H, m)

20) 2-Phenyl-4-(4-isopropoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.30 (6H, d), 4.41-4.50 (1H, m), 4.99 (1H,s), 6.82-6.95 (7H, m), 7.36-7.51 (5H, m)

21) 2-Isopropyl-4-(4-phenoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.24 (6H, d), 3.15-3.24 (1H, m), 4.57 (1H,s), 6.71-7.34 (12H, m)

22) 2,5-Dichloro-4-(4-isopropoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.33 (6H, d), 4.43-4.51 (1H, m), 5.37 (1H,brs), 6.82-6.90 (4H, m), 6.92 (1H, s), 7.13 (1H, s)

23) 2-Allyl-4-(4-isopropoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.32 (6H, d), 3.35-3.38 (2H, m), 4.41-4.51(1H, m), 4.77 (1H, s), 5.11-5.20 (2H, m), 5.91-6.07 (1H, m), 6.73-6.91(7H, m)

24) 2-n-Propyl-4-(3-methoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 0.97 (3H, t), 1.57-1.69 (2H, m), 2.56 (2H,t), 3.77 (3H, s), 4.67 (1H, s), 6.49-7.20 (7H, m)

25) 2-Isopropyl-4-(3-methoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.23 (6H, d), 3.13-3.23 (1H, m), 3.76 (3H,s), 4.67 (1H, s), 6.50-7.21 (7H, m)

26) 2-n-Propyl-4-(3-isopropoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 0.96 (3H, t), 1.31 (3H, d), 1.56-1.69 (2H,m), 2.55 (2H, t), 4.44-4.52 (1H, m), 4.55 (1H, s), 6.47-7.18 (7H, m)

27) 2-Isopropyl-4-(3-biphenyloxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.24 (6H, d), 3.15-3.26 (1H, m), 4.62 (1H,s), 6.71-7.57 (12H, m)

28) 2-Trifluoromethyl-4-(3-chlorophenoxy)phenol

n_(D) ²³.5 1.5316

29) 2-Trifluoromethyl-4-(4-ethoxyphenoxy)phenol

n_(D) ²³.5 1.5322

30) 2-Trifluoromethyl-4-(4-trifluoromethylphenoxy)phenol m.p., 63.1° C.

31) 2-Trifluoromethyl-4-(4-trifluoromethoxyphenoxy)phenol n_(D) ²³.51.4910

32) 2-Trifluoromethyl-4-(4-methoxyphenoxy)phenol

33) 2-Trifluoromethyl-4-(3,4-dimethoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) 8 (ppm): 3.84 (3H, s), 3.89 (3H, s), 5.46 (1H, br),6.50 (1H, dd), 6.60 (1H, d), 6.82 (1H, d), 6.90 (1H, d), 7.05 (1H, dd),7.14 (1H, d)

34) 2-Trifluoromethyl-4-(3-methoxyphenoxy)phenol

35) 2-Trifluoromethyl-4-(3,5-dimethoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 3.76 (6H, s), 5.54 (1H, br), 6.10 (2H, d),6.20 (1H, t), 6.92 (1H, d), 7.12 (1H, dd), 7.22 (1H, d)

36) 2-Trifluoromethyl-4-(3,4-methylenedioxyphenoxy)phenol

37) 2-Trifluoromethyl-4-(3-ethoxy-4-methoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.45 (3H, t), 3.87 (3H, s), 4.05 (2H, q),5.58 (1H, brs), 6.49 (1H, dd), 6.60 (1H, d), 6.83 (1H, d), 6.92 (1H, d),7.06 (1H, dd), 7.16 (1H, d)

38) 2-Trifluoromethyl-4-(2-chloro-4-ethoxyphenoxy)phenol

n_(D) ²³.5 1.5448

39) 2-Trifluoromethyl-4-(4-n-propoxyphenoxy)phenol

n_(D) ²³.5 1.5229

40) 2-Trifluoromethyl-4-(4-isopropoxyphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.33 (6H, d), 4.48 (1H, m), 5.37 (1H, br),6.88 (4H, m),6.90 (1H, d), 7.04 (1H, dd), 7.12 (1H, d)

41) 2-Trifluoromethyl-4-(4-n-butoxyphenoxy)phenol

n_(D) ²³.5 1.5186

42) 2-Trifluoromethyl-4-(4-(2,2,2-trifluoroethoxy)phenoxy)phenol m.p.,66.7° C.

43) 2-Trifluoromethyl-4-(3-isopropoxyphenoxy)phenol

n_(D) ²³.5 1.5251

44) 2-Trifluoromethyl-4-(4-cyclohexylphenoxy)phenol m.p., 83.7° C.

45) 2-Trifluoromethyl-4-(3-ethoxyphenoxy)phenol

n_(D) ²³.5 1.5316

46) 2-Trifluoromethyl-4-(4-phenoxyphenoxy)phenol

n_(D) ²³.5 1.5673

47) 2-Trifluoromethyl-4-(4-biphenyloxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.55 (1H, br), 6.90-7.70 (12H, m)

48) 2-Trifluoromethyl-4-(4-cyclopentylphenyl)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.4-2.2 (8H, m), 2.97 (1H, m), 5.32 (1H,br), 6.88 (2H, d), 7.20 (2H, d), 6.92 (1H, d), 7.08 (1H, dd), 7.17 (1H,d)

49) 2-Trifluoromethyl-4-(2,6-dichloro-4-trifluoromethylphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.46 (1H, br), 6.80-6.96 (2H, m), 7.04(1H, d), 7.70 (2H, s)

50) 2-Trifluoromethyl-4-(4-methoxythiophenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 2.50 (3H, s), 5.72 (1H, br), 6.88 (2H, d),7.28 (2H, d), 6.92 (1H, d), 7.08 (1H, dd), 7.19 (1H, d)

51) 2,5-Dichloro-4-(2,6-dichloro-4-trifluoromethylphenoxy)phenol m.p.,110.2° C.

52) 2-Trifluoromethyl-4-(3-biphenyloxy)phenol

n_(D) ²³.5 1.5872

53) 2,6-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyl)aminophenolm.p., 158.6° C.

54) 2-Trifluoromethyl-4-(4-sec-butylphenoxy)phenol

n_(D) ²³.5 1.5218

55) 2-Trifluoromethyl-4-(4-(1-hydroxypropyl)phenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 0.93 (3H, t), 1.80 (2H, m), 4.60 (1H, t),5.54 (1H, br), 6.93 (1H, d), 7.10 (1H, dd), 7.19 (1H, d), 6.93 (2H, d),7.32 (2H, d)

56) 2-Trifluoromethyl-4-(4-(1-methylbutyl)phenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 0.65-1.00 (5H, m), 1.15-1.40 (5H, m), 2.68(1H, m), 5.46 (1H, br), 6.80-7.40 (7H, m)

57) 2-Trifluoromethyl-4-(4-(1,1-dimethylpropyl)phenoxy)phenol

n_(D) ²³.5 1.5182

58) 2-Trifluoromethyl-4-(4-(1,1,3,3-tetramethylbutyl)phenoxy)phenol

n_(D) 23.5 1.4113

59) 2-Trifluoromethyl-4-(4-tert-butylphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.31 (9H, s), 5.32 (1H, br), 6.87 (2H, d),7.33 (2H, d), 6.93 (1H, d), 7.10 (1H, ddd), 7.19 (1H, d)

60) 2-Trifluoromethyl-4-(3-tert-butylphenoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.30 (9H, s), 5.34 (1H, br), 6.70 (1H, m),6.95 (1H, d), 7.02-7.40 (5H, m)

61) 2-Trifluoromethyl-4-(5,6,7,8-tetrahydro-2-naphthoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.78 (4H, brs), 2.73 (4H, brs), 5.34 (1H,br), 6.60-7.40 (6H, m)

62) 2-Trifluoromethyl-4-(2-naphthoxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.38 (1H, br), 6.60-7.96 (10H, m)

63) 2-Bromo-4-(3-chloro-5-trifluoromethylpyridyloxy)phenol m.p., 101.3°C.

64) 2-Trifluoromethyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.79 (1H, br), 7.02 (1H, d), 7.26 (1H,dd), 7.37 (1H, d), 8.00 (1H, brs), 8.29 (1H, brs)

65) 3-Chloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.89 (1H, s), 6.79 (1H, dd), 6.93 (1H, d),7.10 (1H, d), 8.05 (1H, br), 8.28 (1H, br)

66) 2,5-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.99 (1H, s), 7.11 (1H, s), 7.20 (1H, s),7.93 (1H, brs), 8.20 (1H, brs)

67) 3,5-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.81 (1H, s), 6.89 (2H, s), 8.02 (1H,brs), 8.27 (1H, brs)

68) 2,6-Dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.94 (1H, br), 7.18 (2H, s), 7.99 (1H,brs), 8.30 (1H, brs)

69) 2-Chloro-4-(3,5-bis(trifluoromethyl)-2-pyridyloxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.60 (1H, brs), 7.02 (1H, dd), 7.08 (1H,d), 7.21 (1H, d), 8.21 (1H, brs), 8.55 (1H, brs)

70) 3-Chloro-4-(3,5-bis(trifluoromethyl)-2-pyridyloxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.36 (1H, s), 6.82 (1H, dd), 6.98 (1H, d),7.10 (1H, d), 8.24 (1H, brs), 8.55 (1H, brs)

71) 2,5-Chloro-4-(3,5-bis(trifluoromethyl)-2-pyridyloxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.60 (1H, br), 7.19 (1H, s), 7.28 (1H, s),8.22 (1H, brs), 8.54 (1H, brs)

72) 3-Methyl-4-(3,5-bis(trifluoromethyl)-2-pyridyloxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 2.13 (3H, s), 5.04 (1H, brs), 6.72 (1H,dd), 6.76 (1H, d), 6.96 (1 H, d), 8.23 (1H, brs), 8.54 (1H, brs)

73) 2,6-Dichloro-4-(3,5-bis(trifluoromethyl)-2-pyridyloxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.89 (1H, br), 7.18 (2H, s), 8.24 (1H,brs), 8.59 (1H, brs).

74) 3,5-Dichloro-4-(3,5-bis(trifluoromethyl)-2-pyridyloxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.75(1H, br), 6.90 (2H, s), 8.24 (1H,brs), 8.52 (1H, brs)

75) 2,5-Dichloro-4-(3-bromo-5-trifluoromethyl-2-pyridyloxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.64 (1H, br), 7.17 (1H, s), 7.28 (1H, s),8.16 (1H, brs), 8.30 (1H, brs)

76) 3,5-Dichloro-4-(3-bromo-5-trifluoromethyl-2-pyridyloxy)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 6.20 (1H, brs), 6.86 (2H, s), 8.70 (1H,d), 8.80 (1H, b)

77) 4-(4-Chlorophenylthio)-2-bromophenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.60 (1H, brs), 7.00 (1H, d, J=8.4 Hz),7.14 (2H, d, J=8.7 Hz), 7.23 (2H, d, J=8.4 Hz), 7.30 (1H, dd, J=2.2, 8.4Hz 7.56 (1H, d, J=2.2 Hz)

78) 4-(1-(4-Ethoxyphenyl)-1-methylethyl)-2-bromophenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.40 (3H, t), 1.61 (6H, s), 4.01 (2H, q),6.80 (2H, d, J=8.6 Hz), 6.90 (1H, d, J=8.3 Hz), 7.04 (1H, dd, J=2.4, 8.2Hz), 7.11 (2H, d, J=8.4 Hz), 7.32 (1H, dd, J=2.4 Hz)

79) 4-(4-Ethoxyphenylthio)-2-bromophenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.41(3H, t, J=7.0 Hz), 4.02 (2H, q, J=7.0Hz), 6.85 (2H,d, J=8.0 Hz), 6.92 (1H, d, J=8.5 Hz), 7.15 (1H, dd, J=2.2,8.5 Hz), 7.31 (2H, d, J=8.0 Hz), 7.39 (1H, d, J=2.1 Hz)

80)4-(1-(4-Ethoxyphenyl)-1-(trifluoromethyl)-2,2,2-trifluoroethyl)-2,5-dibromophenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.41 (3H, t), 4.07 (2H, q), 6.04 (1H,brs), 6.89 (2H, d, J=9.7 Hz), 7.27 (2H, d, J=9.6 Hz), 7.48 (2H, s)

81) 4-(4-Methoxyphenylthio)-2-(trifluoromethyl)phenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 3.78 (3H, s), 5.10 (1H, brs), 6.84 (1H, d,J=9.2 Hz), 6.88 (2H, d, J=8.8 Hz), 7.29 (1H, dd, J=2.2, 9.2 Hz), 7.32(2H, d, J=8.8 Hz), 7.47 (1H, d, J=2.2 Hz)

82) 4-(4-Isopropyloxyphenylthio)-2-bromophenol

1H-NMR (CDCl₃ /TMS) δ (ppm): 1.33 (6H, d), 4.53 (1 H, sep), 5.45 (1H,s), 6.83 (2H, d), 6.92 (1H, s), 7.16 (1H, dd), 7.29 (2H, d), 7.40 (1H,d)

83) 4-(1-(4-Isopropyloxyphenyl)-1-methylethyl)-2-bromophenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.33 (6H, d), 1.61 (6H, s), 4.51 (1H,sep), 6.82 (2H, d), 6.91 (1H, d), 7.05 (1H, dd), 7.11 (2H, d), 7.32 (1H,d)

84) 4-(4-Isopropyloxyphenyl)-methyl-2-bromophenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.33 (6H, d), 3.82 (2H, s), 4.52 (1H,sep), 5.42 (1H, s), 6.83 (2H, d), 6.94 (1H, d), 7.05 (1H, dd), 7.07 (2H,d), 7.27 (1H,d)

85) 4-(1-(4-Isopropyloxyphenyl)-ethyl)-2-bromophenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.36 (6H, d), 1.60 (3H, d), 4.05 (1H, q),4.56 (1H, sep), 5.46 (1H, brs), 6.85 (2H, d), 6.96 (1H, d), 7.10 (1H,dd), 7.13 (2H, d), 7.33 (1H, d)

86)4-(N-(3-chloro-5-(trifluoromethyl)-2-pyridyl)amino)-2,5-dichlorophenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 5.75 (1H, brs), 7.12 (1H, s), 7.62 (1H,s), 7.80 (1H, s), 8.40 (1H, s), 8.52 (1H, s)

87) 4-(1-(4-Isopropoxyphenyl)-1-methylethyl)-2-chlorophenol

¹ H-NMR (CDCl₃ /TMS) δ (ppm): 1.33 (6H. s), 1.62 (6H, s), 5.43 (1H, s),6.78 (2H, d). 6.89 (1H, d), 7.02 (1H, dd), 7.11 (2H, d), 7.18 (1H, d)

88) 2-Trifluoromethyl-4-(3-trifluoromethylphenoxy)phenol

89) 2-Trifluoromethyl-4-(3-phenoxyphenoxy)phenol

n_(D) ²³.5 1.5679

The following will describe Formulation Examples. In these FormulationExamples, "parts" are by weight unless otherwise stated.

FORMULATION EXAMPLE 1

Emulsifiable concentrates

Ten parts of each of the compounds 1 to 367 are separately dissolved in35 parts of xylene and 35 parts of dimethylformamide. Each of theresultant mixtures is mixed with 14 parts of polyoxyethylenestyrylphenyl ether and 6 parts of calcium dodecylbenzenesulfonate, andstirred sufficiently to give 10% emulsifiable concentrates for eachcompound.

FORMULATION EXAMPLE 2

Wettable powders

Twenty parts of each of the compounds 1 to 367 are separately added to amixture of 4 parts of sodium lauryl sulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silicon hydroxide fine powderand 54 parts of diatomaceous earth, and stirred with a mixer to give 20%wettable powders for each compound.

FORMULATION EXAMPLE 3

Granular

To 5 parts of each of the compounds 1 to 367 are added 5 parts ofsynthetic hydrated silicon hydroxide fine powder, 5 parts of sodiumdodecylbenzenesulfonate, 30 parts of bentonite and 55 parts of clay, andstirred sufficiently. Then, a suitable amount of water is added to themixture which is further stirred, granulated with a granulated and thenair-dried to give a 5% granular for each compound.

FORMULATION EXAMPLE 4

Dusts

One part of each of the compounds 1 to 367 separately dissolved in asuitable amount of acetone is mixed with 5 parts of synthetic hydratedsilicon hydroxide fine powder, 0.3 parts of PAP and 93.7 parts of clay.Then, the mixture was stirred with a mixer and acetone is removed togive 1% dusts for each compound.

FORMULATION EXAMPLE 5

Flowables

Twenty parts of each of the compounds 1 to 367 are separately mixed with1.5 parts of sorbitan trioleate and 28.5 parts of an aqueous solutioncontaining 2 parts of polyvinyl alcohol, and the mixture is pulverizedinto fine particles having a particle size of not more than 3 μm with asand grinder. Each of the mixture was mixed with 40 parts of an aqueoussolution containing 0.05 parts of xanthan gum and 0.1 parts of aluminummagnesium silicate, and then mixed with 10 parts of propylene glycol togive 20% water-based suspensions for each compound.

FORMULATION EXAMPLE 6

Oil solutions

First, 0.1 parts of each of the compounds 1 to 367 are separatelydissolved in 5 parts of xylene and 5 parts of trichloroethane. Then, thesolution was mixed with 89.8 parts of deodorized kerosine to give 0.1%oil solutions for each compound.

FORMULATION EXAMPLE 7

Oil-based aerosol

First, 0.1 parts of each of the compounds 1 to 367, 0.2 parts oftetramethrin, 0.1 parts of d-phenothrin, 10 parts of trichloroethane aredissolved in 59.6 parts of deodorized kerosine, and an aerozol vessel isfilled with the solution. Then, the vessel is equipped with a valve,through which 30 parts of a propellant (liquefied petroleum gas) arecharged under pressure to give an oil-based aerosol of each compound.

FORMULATION EXAMPLE 8

Water-based aerosol

An aerosol vessel is filled with 50 parts of pure water and a mixture of0.2 parts of each of the compounds 1 to 367, 0.2 parts of d-allethrin,0.2 parts of d-phenothrin, 5 parts of xylene, 3.4 parts of deodorizedkerosine and 1 part of an emulsifier ATMOS 300 (registered trade mark byAtlas Chemical Co.)!. Then, the vessel is equipped with a valve, throughwhich 40 parts of a propellant (liquefied petroleum gas) are chargedunder pressure to give a water-based aerosol of each compound.

FORMULATION EXAMPLE 9

Mosquito-coil

First, 0.3 g of each of the compounds 1 to 367 and 0.3 g of d-allethrinare dissolved in 20 ml of acetone, and the solution is mixed uniformlywith 99.4 g of a carrier for mosquito-coil (prepared by mixing Tabupowder, dregs powder and wood flour in the ratio of 4:3:3) withstirring. Then, 120 ml of water is added to the mixture, which iskneaded sufficiently, molded and dried to give a mosquito-coil of eachcompound.

FORMULATION EXAMPLE 10

Electric mosquito-mat

First, 0.4 g of each of the compounds 1 to 367, 0.4 parts of d-allethrinand 0.4 g of pipenyl butoxide are separately dissolved in acetone togive 10 ml of a solution. A substrate for electric mat having a size of2.5 cm×1.5 cm×0.3 cm in thickness (prepared by forming a fibrillatedmixture of cotton linter and pulp into a sheet) is impregnated uniformlywith 0.5 ml of the solution to give an electric mosquito-mat of eachcompound.

FORMULATION EXAMPLE 11

Heating smoke formulation

First, 100 mg of each of the compounds 1 to 367 is separately dissolvedin a suitable amount of acetone. Then, a porous ceramic plate having asize of 4.0 cm×4.0 cm×1.2 cm in thickness is impregnated with theresultant solution to give a heating smoke formulation of each compound.

FORMULATION EXAMPLE 12

Poison baits

First, 10 mg of each of the compounds 1 to 367 is separately dissolvedin 0.5 ml of acetone, and the solution is mixed uniformly with 5 g ofsolid bait powder (Breeding Solid Feed Powder CE-2, trade name by JapanClea Co., Ltd.). Then, acetone is removed to give a 0.2% poison bait ofeach compound.

The following Biological Test Examples will illustrate that thedihalopropene compounds of the present invention are useful as an activeingredient of insecticides/acaricides. In these Biological TestExamples, the dihalopropene compounds of the present invention aredesignated by the corresponding numbers described above and thecompounds used for comparison are designated by the correspondingsymbols in Table 22.

                  TABLE 22                                                        ______________________________________                                        Symbol                                                                        of com-                                                                       pound Chemical Structure     Remarks                                          ______________________________________                                               ##STR415##            Compound dis- closed in the Japanese Pat-                                     ent Laid-open Publication No. 48-86835/1973      B                                                                                    ##STR416##            Compound dis- closed in the Japanese Pat-                                     ent Laid-open Publication No. 49-1526/1974       ______________________________________                                    

BIOLOGICAL TEST EXAMPLE 1

Insecticidal test against Spodoptera litura

An emulsion was prepared from the test compound according to FormulationExample 1. Then, 13 g of an artificial diet for Spodoptera litura, whichwas prepared in a polyethylene cup having a diameter of 11 cm inadvance, was impregnated with 2 ml of a 200-folded diluted solution ofthe emulsion (500 ppm) in water. Ten fourth instar larvae of Spodopteralitura were set free in the cup. After six days, the survival of larvaewas examined to determine the mortality in duplicate.

As a result, it was found that the compounds 1-3, 6-14, 16-21, 23-28,31-33, 36-45, 47-62, 64-69, 76-78, 80, 84, 86-90, 92-97, 103-114,116-122, 124, 125, 127-133, 135, 136, 138-185, 189-216, 218-224,226-233,236, 237, 239-242, 244-246, 248-253, 262, 265, 266, 267, 271,273-280, 292-294, 297-303, 305, 309-313, 316, 317, 319-321,323, 329-336,338, 339, 347, 349-356, 359-361, 363, 366 and 367 exhibited themortality of not less than 80%. In contrast, the compounds A and Bexhibited the mortality of 0%.

BIOLOGICAL TEST EXAMPLE 2

Test against Tetranychus urticae Koch

Ten Female imagines of Tetranychus urticae Koch per one leaf wereallowed to parasitize to a poring bean harvested for 7 days afterseeding (primary leaf stage), which was placed in a greenhousemaintained at 25° C. After 6 days, 15 ml of a chemical solution(containing 500 ppm of an active ingredient), which was prepared bydiluting an emulsion of the test compound obtained according toFormulation Example 1 with water, was sprayed over a pot on a turntable.At the same time, 2 ml of the same solution was drenched in the soil.After 8 days, the degree of damage of the respective plants caused byTetranychus urticae Koch was examined. The activity was evaluatedaccording to the criteria:

-: Damage is scarcely observed.

+: Damage is slightly observed.

++: Damage is observed at the same level as in the non-treated field.

As a result, it was found that the compounds 1, 5-9, 12, 13, 19, 21-28,31-38, 41-49, 51, 53, 55-63, 65-73, 75, 76, 79-86, 89-91, 93, 97,100-108, 110, 115, 126-130, 136-151, 155-158, 163-165, 169, 179-181,183, 188, 190, 191, 193, 196, 197, 200, 202, 210-213, 215, 236-239,242-244, 247,250, 252-255, 257-262, 265, 266, 268, 270-274, 276, 277,279, 280, 291-296, 303, 305, 309, 310, 318, 319, 323, 329-331, 333,340-343, 348 and 363 were evaluated as "-" or "+". In the contrast, thecompounds A and B were evaluated as "++".

What is claimed is:
 1. An intermediate compound of the formula:##STR417## wherein l is an integer of 1 to 5; R¹ is halogen, C₁ -C₈alkyl, trifluoromethyl, C₁ -C₄ alkoxy, C₁ -C₂, C₃ -C₅ alkenyloxy, C₃ -C₄haloalkenyloxy, C₃ -C₆ cycloalkyl, phenyl, pyridyloxy, phenoxy orbenzyl, the last four of which may be optionally substituted withhalogen, C₁ -C₅ alkyl, C₁ -C₃ alkoxy, C₁ -C₃ haloalkyl or C₁ -C₃haloalkoxy, with the proviso that when l is an integer of 2 to 5, R¹ 'sare the same or different, and when l is an integer of 1 to 3, twoadjacent R¹ 's may be combined together at their terminal ends to formtrimethylene, tetramethylene, methylenedioxy, ethylenedioxy orCH═CH--CH═CH.
 2. An intermediate compound of the formula: ##STR418##wherein R¹ is halogen or trifluoromethyl; R² 's are the same ordifferent and are independently halogen, trifluoromethyl or C₁ -C₃alkyl; and m is an integer of 1 to
 4. 3. An intermediate compoundaccording to claim 1, which is2-trifluoromethyl-4-(4-isopropoxyphenoxy)phenol.
 4. An intermediatecompound according to claim 1, which is2-trifluoromethyl-4-(4-cyclohexylphenoxy)phenol.
 5. An intermediatecompound according to claim 1, which is2-trifluoromethyl-4-(2,6-dichloro-4-trifluoromethylphenoxy)phenol.
 6. Anintermediate compound according to claim 1, which is2-trifluoromethyl-4-(5,6,7,8-tetrahydro-2-naphthyloxy)phenol.
 7. Acompound which is3,5-dichloro-4-(3,5-bistrifluoromethyl-2-pyridyloxy)phenol.
 8. Anintermediate compound according to claim 2, which is2,6-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridylamino)phenol.